Silicon-containing olefin copolymer, crosslinkable rubber composition thereof, and use thereof

ABSTRACT

A silicon-containing olefin copolymer is provided which comprises (a) a constituent unit derived from —CH 2 —CH 2 — such as ethylene, (b) a constituent unit derived from —CH 2 —CHR— where R is a hydrocarbon group of 1 to 18 carbon atoms, and (c) a constituent unit containing a specific silicon-containing group. A silicon-containing olefin copolymer is also provided which is obtainable by co-polymerizing ethylene, an a-olefin of 3 to 20 carbon atoms and a specific silicon-containing ethylene monomer.

FIELD OF THE INVENTION

The present invention relates to a silicon-containing olefin copolymer,a cross-linkable rubber composition of the copolymer and uses thereof.More specifically, it relates to a cross-linkable (vulcanizable) olefincopolymer containing constituent units derived from a silicon compoundas a site for cross-linking, its cross-linkable rubber composition andits uses.

BACKGROUND OF THE INVENTION

Ethylene/α-olefin random copolymers such as EPDM and the like generallyhave excellent weathering resistance, heat resistance and ozoneresistance, and used for electrical wire-covering materials such aselectric power cables, cabtyre cords, electric wires for ships, electricinsulating rubber tapes, rubber-mold stress cones, electric joint partsand the like, home electric insulating parts such as anode caps, wedgesand the like, electric insulating parts for automobiles such as plugcaps, grommets, ignition cables, lamp socket covers and the like,terminal covers and semiconductor rubber parts.

Conventional ethylene/α-olefin random copolymers have a defect such thatit is inferior in resistance to compression set as compared with siliconrubber etc. To cope with this defect, a method of peroxide cross-linkingis more effective than that of sulfur vulcanization. This method,however, has defects that when hot air cross-linking with HAV (hot airvulcanization vessel), UHF (ultra high frequency electromagnetic wave),etc is employed, the surface of a rubber is not cross-linked, ordegradation is induced and thereby the scratch resistance of the rubberis extremely deteriorated. The defects are due to the reason thatperoxide does not participate in cross-linking and the rubber surfacecontacts oxygen and thereby degradation proceeds. When the cross-linkingis conducted by steam cross-linking with shutting oxygen off or by leadcovering cross-linking, the scratch resistance of the rubber surface isimproved but the production cost is disadvantageous.

JP-A-H04-154855 discloses a process for preparing a hot aircross-linkable rubber having excellent scratch resistance by using, in aHAV, a rubber composition which comprises a hot air cross-linkableethylene/propylene/diene copolymer rubber, organohydrodiene polysiloxanehaving at least two hydrogen atoms bonded with a silicon atom in amolecule, and a platinum catalyst.

However, on testing the invention disclosed in this publication, thepresent inventors found that the scratch resistance and the resistanceto compression set were not sufficiently satisfactory for them.

JP-A-H07-33924 discloses a process for preparing a hot aircross-linkable rubber having excellent scratch resistance by peroxidecross-linking a rubber composition, which is obtainable by addingpolysiloxane having at least one reactive group to anethylene/propylene/diene copolymer rubber.

However, on testing the invention disclosed in this publication, thepresent inventors found that the cross-linking efficiency is enhanceddue to adding of peroxide to the rubber composition, but the scratchresistance of the surface of a rubber molded article after cross-linkingis not suitable for practical use because peroxide radicals causeaddition reaction of siloxane and also generation of polymer radicals.

Further, JP-A-2001-31808 discloses a polyene-containing copolymercapable of being modified with SiH group. In the polyene containing avinyl group capable of being modified with SiH group, most of the vinylgroups are used for forming a long chain branch and a part of vinylgroups is only used for the reaction with SiH group so that theefficiency is low. Additionally, the generation of long chain branchescauses a lowering of the rubber strength.

Accordingly, the advent of an olefin copolymer having a highcross-linking rate, excellent productivity and capable of preparingmolded articles having excellent resistance to compression set, electricproperties, strength and other properties, a preparation process thereofand a cross-linkable rubber composition of the copolymer has beendesired.

The present invention is intended to solve the problems associated withthe prior art as mentioned above, and it is an object of the presentinvention to provide an olefin copolymer having a high cross-linkingrate, excellent productivity and capable of preparing molded articleshaving excellent resistance to compression set, electric properties,strength and other properties. It is another object of the presentinvention to provide a cross-linkable rubber composition of thecopolymer. It is a further object of the present invention to provideuses thereof including sealing materials, potting materials, coatingmaterials, adhesives and the like.

DISCLOSURE OF THE INVENTION

The first silicon-containing olefin copolymer of the present inventioncomprises:

-   (a) a constituent unit derived from —CH₂—CH₂—,-   (b) a constituent unit derived from —CH₂—CHR— [R is a hydrocarbon    group of 1 to 18 carbon atoms], and-   (c) a constituent unit represented by the following formula (I)    wherein k is 0, 1 or 2,-   A is a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms,-   B is a single bond or a hydrocarbon group of 1 to 20 carbon atoms,-   X, Y, and Z are each independently selected from a hydrocarbon group    of 1 to 6 carbon atoms, hydride, halogen, alkoxy group of 1 to 6    carbon atoms, acyloxy group, ketoximate group, amide group, acid    amide group, aminoxy group, thioalkoxy group and amino group, at    least one of X, Y and Z is selected from a halogen, an alkoxy group    of 1 to 6 carbon atoms, acyloxy group, ketoximate group, amide    group, acid amide group, aminoxy group, thioalkoxy group and amino    group,

and the first silicon-containing olefin copolymer has:

-   (i) a molar ratio [(a)/(b)] of the constituent unit (a) to the    constituent unit (b) of from 99/1 to 30/70,-   (ii) a content of the constituent unit (c) of from 0.1 to 10 mol %    based on 100 mol % of the total amounts of the constituent units    (a), (b) and (c), and-   (iii) a branching index of not less than 0.70.

In the silicon-containing olefin copolymer, the constituent unit (c) ispreferably represented by the formula (I) in which k is o, A is ahydrogen atom and B is represented by —(CR¹R²)_(n)—, namely representedby the following formula (II)

In the formula, n is an integer of 0 to 10,

R¹ and R² each are independently a hydrogen atom or an alkyl group of 1to 3 carbon atoms, and when n is 2 or more, the plural groups R¹ may beidentical or different each other and also the plural groups R² may beidentical or different each other.

Furthermore, in the first silicon-containing olefin copolymer of thepresent invention, the constituent unit (c) is preferably represented bythe formula (I) in which k is 1, A is a hydrogen atom and B isrepresented by —(CR¹R²)_(n)—, namely represented by the followingformula (III)

In the formula, n is an integer of 0 to 10,

R¹ and R² each are independently a hydrogen atom or an alkyl group of 1to 3 carbon atoms, and when n is 2 or more, the plural groups R¹ may beidentical or different each other and also the plural groups R² may beidentical or different each other.

The second silicon-containing olefin copolymer of the present inventionis obtainable by copolymerizing ethylene, an α-olefin of 3 to 20 carbonatoms and an ethylene monomer having a silicon-containing grouprepresented by the following formula (IV):—Si(X)(Y)(Z)  (IV)

wherein X, Y, and Z are each independently selected from a hydrocarbongroup of 1 to 6 carbon atoms, hydride, halogen, alkoxy group of 1 to 6carbon atoms, acyloxy group, ketoximate group, amide group, acid amidegroup, aminoxy group, thioalkoxy group and amino group, at least one ofX, Y and Z is selected from a halogen, an alkoxy group of 1 to 6 carbonatoms, acyloxy group, ketoximate group, amide group, acid amide group,aminoxy group, thioalkoxy group and amino group,

and the second silicon-containing olefin copolymer has:

-   (i) a molar ratio [ethylene/α-olefin] of ethylene to α-olefin of 3    to 20 carbon atoms of from 99/1 to 30/70,-   (ii) a content of the ethylene monomer having a silicon-containing    group of from 0.1 to 10 mol % based on 100 mol % of the total    amounts of ethylene, α-olefin and the ethylene monomer having a    silicon-containing group of the formula (IV), and-   (iii) a branching index of not less than 0.70.

The first and second silicon-containing olefin copolymers according tothe present invention preferably have an intrinsic viscosity [η], asmeasured in decalin at 135° C., of from 0.1 to 10 dl/g.

The first and second silicon-containing olefin copolymers according tothe present invention preferably satisfy the following formula:IV<33800/Mn

wherein Mn is a number average molecular weight and IV is an iodinevalue.

In the present invention, the first and second silicon-containing olefincopolymers may be occasionally overlapped or not.

The cross-linkable rubber composition of the present invention comprisesany one of the silicon-containing olefin copolymers as described in theabove.

The cross-linkable rubber composition of the present invention ispreferably used for electric and electronic parts, transportingmachines, civil engineering and constructions, medical treatment orleisure activity use.

The cross-linkable rubber composition of the present invention ispreferably used for sealing materials, potting materials, coatingmaterials and adhesives.

The sealing materials, potting materials, coating materials andadhesives according to the present invention comprise the abovecross-linkable rubber composition.

The cross-linked product of the present invention is obtainable bycross-linking the above cross-linkable rubber composition.

PREFERRED EMBODIMENTS OF THE INVENTION

The silicon-containing olefin copolymer, its cross-linkable rubbercomposition and the uses thereof according to the present invention willbe described in detail hereinafter.

First, the silicon-containing olefin copolymer and the preparationprocess thereof are described.

Silicon-Containing Olefin Copolymer

The first silicon-containing olefin copolymer of the present inventioncomprises:

-   (a) a constituent unit derived from —CH₂—CH₂—,-   (b) a constituent unit derived from —CH₂—CHR— [R is a hydrocarbon    group of 1 to 18 carbon atoms], and-   (c) a constituent unit represented by the formula (I) as described    later, and has:-   (i) a molar ratio [(a)/(b)] of the constituent unit (a) to the    constituent unit (b) of from 99/1 to 30/70,-   (ii) a content of the constituent unit (c) of from 0.1 to 10 mol %    based on 100 mol % of the total amounts of the constituent units    (a), (b) and (c), and-   (iii) a branching index of not less than 0.70.

One of the constituent units of the first silicon-containing olefincopolymer of the present invention is a constituent unit (a) representedby —CH₂—CH₂—.

Another constituent unit of the first silicon-containing olefincopolymer of the present invention is a constituent unit (b) representedby —CH₂—CHR—.

In the formula, R is a hydrocarbon group of 1 to 18 carbon atoms.Examples the hydrocarbon group may include alkyl groups such as methyl,ethyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.Among them, R is preferably a hydrocarbon groups of 1 to 8 carbon atoms,and particularly preferably methyl, ethyl, n-butyl or n-hexyl. Thesegroups R may be present singly or in combination with two or more.

A further constituent unit of the first silicon-containing olefincopolymer of the present invention is a constituent unit (c) representedby the following formula

In the formula (I), k is 0, 1 or 2,

-   A is a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms,-   B is a single bond or a hydrocarbon group of 1 to 20 carbon atoms,-   X, Y, and Z are each independently selected from a hydrocarbon group    of 1 to 6 carbon atoms, hydride, halogen, alkoxy group of 1 to 6    carbon atoms, acyloxy group, ketoximate group, amide group, acid    amide group, aminoxy group, thioalkoxy group and amino group. At    least one of X, Y and Z is a group or atom selected from a halogen,    alkoxy group of 1 to 6 carbon atoms, acyloxy group, ketoximate    group, amide group, acid amide group, aminoxy group, thioalkoxy    group and amino group.

A of the formula (I) showing the constituent unit (c) is a hydrogen atomor a hydrocarbon group of 1 to 6 carbon atoms. Examples of thehydrocarbon group of 1 to 6 carbon atoms may include aliphatichydrocarbon groups such as methyl, ethyl, propyl, butyl etc; aromatichydrocarbon groups such as phenyl, etc; alicyclic hydrocarbon groupssuch as cyclohexyl group, etc. Particularly, A is preferably a hydrogenatom.

B of the formula (I) is a hydrocarbon group of 1 to 20 carbon atoms.Examples of the hydrocarbon group of 1 to 20 carbon atoms, which is notparticularly limited as far as it is a divalent hydrocarbon group, mayinclude aliphatic hydrocarbon groups formed from an alkylene group suchas —CH₂—, —CH₂—CH₂—, etc, aromatic hydrocarbon groups such as phenylene,etc; and alicyclic hydrocarbon groups such as cyclohexylene.

X,Y and Z each are independently a group or atom selected from ahydrocarbon group of 1 to 6 carbon atoms, hydride, halogen, alkoxy groupof 1 to 6 carbon atoms, acyloxy group, ketoximate group, amide group,acid amide group, aminoxy group, thioalkoxy group and amino group.

Preferable examples of the hydrocarbon group of 1 to 6 carbon atoms arealkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl, sec-butyl, pentyl and hexyl. Of these, alkylgroups of 1 to 3 carbon atoms are preferably used from the viewpoint ofseparation of residual monomers from a copolymer and cross-linkingefficiency.

Examples of the alkoxy group of 1 to 6 carbon atoms are methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy,pentyloxy and hexyloxy. Of these, alkoxy groups of 1 to 3 carbon atomsare preferably used from the viewpoint of separation of residualmonomers from a copolymer and cross-linking efficiency.

Examples of the halogen are chlorine, fluorine, bromine and iodineatoms.

Examples of the acyloxy group are acetoxy and benzoyloxy groups.

Examples of the ketoximate group are acetoxymate, dimethyl ketoximate,diethyl ketoximate and cyclohexylmate groups.

Examples of the amide group are dimethylamide, diethylamide,dipropylamide, dibutylamide and diphenylamide groups.

Examples of the acid amide group are carboxylic acid amide, maleic acidamide, acrylic acid amide and itaconic acid amide groups.

Examples of the thioalkoxy group are thiomethoxy, thioethoxy,thiopropoxy, thioisopropoxy, thioisobutoxy, sec-thiobutoxy,tert-thiobutoxy, thiopentyloxy, thiohexyloxy and thiophenoxy groups.

Examples of the amino group are dimethylamino, diethylamino,dipropylamino, dibutylamino and diphenylamino groups.

Of these, alkoxyl groups, particularly, alkoxyl groups of 1 to 4 carbonatoms are preferred.

In the formula (I) showing the constituent unit (c), at least one of X,Y and Z is a group or atom selected from a halogen, alkoxy group of 1 to6 carbon atoms, acyloxy, ketoximate, amide acid amide, aminoxy,thialkoxy and amino groups.

X, Y and Z, further, each are preferably a group or atom selected from ahydrogen atom, a hydrocarbon group of 1 to 6 carbon atoms, alkoxy groupof 1 to 6 carbon atoms and halogen.

In the most preferable case, X, Y and Z, further, each are preferably agroup or atom selected from a hydrogen atom, a hydrocarbon group of 1 to6 carbon atoms, alkoxy group of 1 to 6 carbon atoms and halogen, and atleast one of X, Y and Z is an alkoxy group or a halogen atom.

Further, among the above groups and atoms, X, Y and Z each arepreferably a group or atom other than a hydrogen atom.

Examples of the silyl group represented by the formula —SiXYZ mayinclude trimethoxy silyl, methyl dimethoxy silyl, dimethyl methoxysilyl, dimethoxy dichlorosilyl and triethoxy silyl. The silyl grouprepresented by —SiXYZ is preferably a hydrolyzable group.

In the formula (I), k is 0, 1 or 2. In the case of k=0, the constituentunit (c) is —CHA-CH(BSiXYZ)—. In the case of k=1, the constituent unit(c) is

In the silicon-containing olefin copolymer, the constituent unit (c) ispreferably represented by the formula (I) in which k is 0, A is ahydrogen atom and B is —(CR¹R²)_(n)—, i.e. has a structure representedthe following formula (II):

In the formula (II), n is an integer of 0 to 10, R¹ and R² each areindependently a hydrogen atom, an alkyl group of 1 to 3 carbon atoms.When n is two or more, the plural groups R¹ may be the same or differenteach other and the plural groups R² may be also the same or differenteach other.

R¹ and R² each are independently a hydrogen atom or an alkyl group of 1to 3 carbon atoms.

Examples of the alkyl group of 1 to 3 carbon atoms may include methyl,ethyl, n-propyl and isopropyl groups.

Although n is an integer of 0 to 10, when n is two or more, the pluralgroups R¹ may be the same or different each other and the plural groupsR² may be also the same or different each other. For example, when n is2, it can have a structure of —CH(CH₃)—C(C₂H₅)(C₃H₇)—.

Furthermore, the constituent unit (c) is preferably represented by theformula (I) in which k is 1, A is a hydrogen atom and B is—(CR¹R²)_(n)—, i.e. has a structure represented by the following formula(III):

In the formula (III), n is an integer of 0 to 10, R¹ and R² each areindependently a hydrogen atom, an alkyl group of 1 to 3 carbon atoms.When n is two or more, the plural groups R¹ may be the same or differenteach other and the plural groups R² may be also the same or differenteach other.

Examples of the alkyl group of 1 to 3 carbon atoms may include methyl,ethyl, n-propyl and isopropyl.

Although n is an integer of 0 to 10, when n is two or more, the pluralgroups R¹ may be the same or different each other and the plural groupsR² may be also the same or different each other. For example, when n is2, it can have a structure of —CH(CH₃)—C(C₂H₅)(C₃H₇)—.

Examples of the constituent unit (c) of the formula (II) are listedbelow:

-   —CH₂—CH(CH₂—Si(OMe)₃)—-   —CH₂—CH(CH₂—SiMe(OMe)₂)—-   —CH₂—CH(CH₂—SiMe₂(OMe))—-   —CH₂—CH(CH₂—SiCl(OMe)₂)—-   —CH₂—CH(CH₂—SiCl(OEt)₂)—-   —CH₂—CH(CH₂—CH₂—Si(OMe)₃)—-   —CH₂—CH(CH₂—CH₂—SiMe(OMe)₂)—-   —CH₂—CH(CH₂—CH₂—SiMe₂(OMe))—-   —CH₂—CH(CH₂—CH₂—SiCl(OMe)₂)—-   —CH₂—CH(CH₂—CH₂—SiCl(OEt)₂)—-   —CH₂—CH(CH₂—CH₂—CH₂—Si(OMe)₃)—-   —CH₂—CH(CH₂—CH₂—CH₂—SiMe(OMe)₂)—-   —CH₂—CH(CH₂—CH₂—CH₂—SiMe₂(OMe))—-   —CH₂—CH(CH₂—CH₂—CH₂—SiCl(OMe)₂)—-   —CH₂—CH(CH₂—CH₂—CH₂—SiCl(OEt)₂)—

In the above formulas, Me is a methyl group and Et is an ethyl group.

In addition to the above constituent units, constituent units derivedfrom a silicon-containing ethylene monomer obtainable by allowing acyclopentadiene or dicyclopentadiene to react with a silicon-containingolefin compound represented by the formula (VII) as described later canbe exemplified.

The first silicon-containing olefin copolymer of the present inventionmay contain constituent units other than the above constituent unitswithin the limit of not deteriorating the object of the invention.

Examples of the constituent units are:

in the formulas, n is an integer of 1 to 10.

Further, the first silicon-containing olefin copolymer of the presentinvention may contain small amounts of the constituents having thefollowing structures:

(Herein, in the indication “C—”, the adjacent substituent of C— isabbreviated and it shows some group such as a hydrocarbon group orpolymer chain and the like.)

For example, the first silicon-containing olefin copolymer of thepresent invention having a branching index of not less than 0.70 maycontain small amounts of the constituent units having the abovestructures. The preferable range of the branching index is as previouslydescribed.

The first silicon-containing olefin copolymer of the present inventioncan be produced by, for example, as described later, copolymerizingethylene, an α-olefin of 3 to 20 carbon atoms and a —SiXYZ groupcontaining ethylene monomer represented by the formula (IV).

The second silicon-containing olefin copolymer of the present inventioncan be produced by, for example, as described later, copolymerizingethylene, an α-olefin of 3 to 20 carbon atoms and a silicon-containinggroup represented by the formula (IV) i.e. —Si(X)(Y)(Z) group containingethylene monomer.

More specifically, the second silicon-containing olefin copolymer of thepresent invention can be produced by copolymerizing ethylene, anα-olefin of 3 to 20 carbon atoms and a silicon-containing ethylenemonomer having a reactive Si structure, and has:

-   (i) a molar ratio [ethylene/α-olefin] of ethylene to α-olefin of 3    to 20 carbon atoms of from 99/1 to 30/70,-   (ii) a content of the ethylene monomer having a silicon-containing    group of from 0.1 to 10 mol % based on 100 mol % of the total    amounts of ethylene, α-olefin and the ethylene monomer, and-   (iii) a branching index of not less than 0.70.

Examples of the α-olefin of 3 to 20 carbon atoms are propylene,1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene,9-methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl-1-tetradecene.Among them, α-olefins of 3 to 10 carbon atoms are preferably used, andparticularly, propylene, 1-butene, 1-hexene and 1-octene are morepreferably used. These α-olefins are used singly or in combination withtwo or more.

The compound having a reactive Si structure constituting the secondsilicon-containing olefin copolymer of the present invention is anethylene monomer having a silicon-containing group represented by theformula (IV)—Si(X)(Y)(Z)  (IV)and specifically is a compound having a structure represented by theformula (V) or (VI):

In the formulas (V) and (VI), R¹ and R² each are independently ahydrogen atom or an alkyl group of 1 to 3 carbon atoms.

Examples of the alkyl group of 1 to 3 carbon atoms may include methyl,ethyl, n-propyl and isopropyl.

Although n is an integer of 0 to 10, when n is two or more, the pluralgroups R¹ may be the same or different each other and the plural groupsR² may be also the same or different each other. For example, when n is2, it can have a structure of —CH(CH₃)—C(C₂H₅)(C₃H₇)—.

In the formulas (IV), (V) and (VI), X, Y and Z each are independently agroup or atom selected from a hydrocarbon group of 1 to 6 carbon atoms,hydride, halogen, alkoxy group of 1 to 6 carbon atoms, acyloxy group,ketoximate group, amide group, acid amide group, aminoxy group,thioalkoxy group and amino group, at least one of X, Y and Z is selectedfrom a halogen, alkoxy group of 1 to 6 carbon atoms, acyloxy group,ketoximate group, amide group, acid amide group, aminoxy group,thioalkoxy group and amino group.

Preferable examples of the hydrocarbon group of 1 to 6 carbon atoms arealkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, tert-butyl, sec-butyl, pentyl and hexyl. Of these, alkylgroups of 1 to 3 carbon atoms are preferably used from the viewpoint ofseparation of residual monomers from a copolymer and cross-linkingefficiency.

Examples of the alkoxy group of 1 to 6 carbon atoms are methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy,pentyloxy and hexyloxy groups. Of these, alkoxy groups of 1 to 3 carbonatoms are preferably used in view of separation of residual monomersfrom a copolymer and cross-linking efficiency.

Examples of the halogen are chlorine, fluorine, bromine and iodineatoms.

Examples of the acyloxy group are acetoxy and benzoyloxy groups.

Examples of the ketoximate group are acetoxymate, dimethyl ketoximate,diethyl ketoximate and cyclohexylmate groups.

Examples of the amide group are dimethylamide, diethylamide,dipropylamide, dibutylamide and diphenylamide groups.

Examples of the acid amide group are carboxylic acid amide, maleic acidamide, acrylic acid amide and itaconic acid amide groups.

Examples of the thioalkoxy group are thiomethoxy, thioethoxy,thiopropoxy, thioisopropoxy, thioisobutoxy, sec-thiobutoxy,tert-thiobutoxy, thiopentyloxy, thiohexyloxy and thiophenoxy groups.

Examples of the amino group are dimethylamino, diethylamino,dipropylamino, dibutylamino and diphenylamino groups.

Of these, alkoxyl groups, particularly, alkoxyl groups of 1 to 4 carbonatoms are preferred.

In the formula (IV) of the silicon-containing group having ethylenemonomer constituting the second silicon-containing olefin copolymeraccording to the present invention, at least one of X, Y and Z isselected from halogen, an alkoxy group of 1 to 6 carbon atoms, acyloxygroup, ketoximate group, amide group, acid amide group, aminoxy group,thioalkoxy group and amino group.

Further, X, Y and Z each are preferably a hydrogen atom, a hydrocarbongroup of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms ora halogen.

In the most desirable case, X, Y and Z each are a hydrogen atom, ahydrocarbon group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6carbon atoms or a halogen and also at least one of X, Y and Z is analkoxy group or a halogen.

Furthermore, among the above groups and atoms, X, Y and Z each arepreferably a group or atom other than a hydrogen atom.

Examples of the silicon-containing ethylene monomer of the formula (V)may include:

allyl group containing compounds such as allyltrimethoxysilane,allylmethyldimethoxysilane, allyldimethylmethoxysilane,allyldimethoxychlorosilane and allyltriethoxysilane;

butenyl group containing compounds such as butenyltrimethoxysilane,butenylmethyldimethoxysilane, butenyldimethylmethoxysilane,butenyldimethoxychlorosilane and butenyltriethoxysilane; and

pentenyl group containing compounds such as pentenyltrimethoxysilane,pentenylmethyldimethoxysilane, pentenyldimethylmethoxysilane,pentenyldimethoxychlorosilane and pentenyltriethoxysilane.

Examples of the silicon-containing group having ethylene monomerrepresented by the formula (VI) are as follows:

The silicon-containing group having ethylene monomer as described abovecan be produced by allowing a silicon-containing olefin compoundrepresented the following formula (VII) to react with dicyclopentadieneor cyclopentadiene.

In the formula (VII), R³ and R⁴ each are independently a hydrogen atom,an alkyl group of 1 to 3 carbon atoms and they may be the same ordifferent each other, and further may vary in accordance with k.

Examples of the alkyl group of 1 to 3 carbon atoms as R³ and R⁴ mayinclude methyl, ethyl, n-propyl and isopropyl.

X, Y and Z are the same as those in the formula (V) and each areindependently an alkoxy group of 1 to 6 carbon atoms, halogen atom,alkyl group of 1 to 6 carbon atoms or hydrogen atom, and at least one ofX, Y and Z is an alkoxy group or halogen atom.

Examples of the alkoxy group of 1 to 6 carbon atoms as X, Y and Zaremethoxy, ethoxy, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.

Examples of the halogen are fluorine, chlorine, bromine and iodineatoms.

Examples of the alkyl group having 1 to 6 carbon atoms may includemethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

K is an integer of 0 to 10, and j is 0 or 1.

Examples of the silicon-containing olefin compound of the formula (VII)may include silicon-containing olefin compounds such as:

-   vinyldimethoxymethylsilane,-   vinyldiethoxymethylsilane,-   vinyldi-n-propylmethylsilane,-   vinyldiisopropylmethylsilane,-   vinyldi-n-butylmethylsilane,-   vinyldiisobutylmethylsilane,-   vinyldimethoxyethylsilane,-   vinyldimethoxy-n-propylsilane,-   vinyldimethoxyisopropylsilane,-   vinyldimethoxyn-butylsilane,-   vinyldimethoxyisobutylsilane,-   vinyldimethoxytert-butylsilane,-   vinyldiethoxyethylsilane,-   vinyldiethoxyn-propylsilane,-   vinyldiethoxyisopropylsilane,-   vinyldimethoxyhydrosilane,-   vinyldiethoxyhydrosilane,-   vinylmethoxydimethylsilane,-   vinylethoxydimethylsilane,-   vinyl-n-propyldimethylsilane,-   vinylisopropyldimethylsilane,-   vinyl-n-butyldimethylsilane,-   vinylisobutyldimethylsilane,-   vinylmethoxydiethylsilane,-   vinylmethoxydi-n-propylsilane,-   vinylmethoxydiisopropylsilane,-   vinylmethoxydi-n-butylsilane,-   vinylmethoxyisodibutylsilane,-   vinylmethoxydi-tert-butylsilane,-   vinylethoxydiethylsilane,-   vinylethoxydi-n-propylsilane,-   vinylethoxydiisopropylsilane,-   vinylmethoxydihydrosilane,-   vinylethoxydihydrosilane,-   vinyldichloromethylsilane,-   vinyldichloroethylsilane,-   vinyldichloro-n-propylsilane,-   vinyldichloroisopropylsilane,-   vinyldichloro-n-butylsilane,-   vinyldichloroisobutylsilane,-   vinyldichlorotert-butylsilane,-   vinyldichlorohydrosilane,-   vinylchlorodimethylsilane,-   vinylchlorodiethylsilane,-   vinylchlorodi-n-propylsilane,-   vinylchlorodiisopropylsilane,-   vinylchlorodi-n-butylsilane,-   vinylchloroisodibutylsilane,-   vinylchlorodi-tert-butylsilane,-   vinylchlorodihydrosilane,-   allyldimethoxymethylsilane,-   allyldiethoxymethylsilane,-   allyldi-n-propylmethylsilane,-   allyldiisopropylmethylsilane,-   allyldi-n-butylmethylsilane,-   allyldiisobutylmethylsilane,-   allyldimethoxyethylsilane,-   allyldimethoxy-n-propylsilane,-   allyldimethoxyisopropylsilane,-   allyldimethoxy-n-butylsilane,-   allyldimethoxyisobutylsilane,-   allyldimethoxytert-butylsilane,-   allyldiethoxyethylsilane,-   allyldiethoxyn-propylsilane,-   allyldiethoxyisopropylsilane,-   allyldimethoxyhydrosilane,-   allyldiethoxyhydrosilane,-   allylmethoxydimethylsilane,-   allylethoxydimethylsilane,-   allyl-n-propyldimethylsilane,-   allylisopropyldimethylsilane,-   allyln-butyldimethylsilane,-   allylisobutyldimethylsilane,-   allylmethoxydiethylsilane,-   allylmethoxydi-n-propylsilane,-   allylmethoxydiisopropylsilane,-   allylmethoxydi-n-butylsilane,-   allylmethoxyisodibutylsilane,-   allylmethoxydi-tert-butylsilane,-   allylethoxydiethylsilane,-   allylethoxydi-n-propylsilane,-   allylethoxydiisopropylsilane,-   allylmethoxydihydrosilane,-   allylethoxydihydrosilane,-   allyldichloromethylsilane,-   allyldichloroethylsilane,-   allyldichloron-propylsilane,-   allyldichloroisopropylsilane,-   allyldichloron-butylsilane,-   allyldichloroisobutylsilane,-   allyldichlorotert-butylsilane,-   allyldichlorohydrosilane,-   allylchlorodimethylsilane,-   allylchlorodiethylsilane,-   allylchlorodi-n-propylsilane,-   allylchlorodiisopropylsilane,-   allylchlorodi-n-butylsilane,-   allylchloroisodibutylsilane,-   allylchlorodi-tert-butylsilane,-   allylchlorodihydrosilane,-   3-butenyldimethoxymethylsilane,-   3-butenyldiethoxymethylsilane,-   3-butenyldi-n-propylmethylsilane,-   3-butenyldiisopropylmethylsilane,-   3-butenyldi-n-butylmethylsilane,-   3-butenyldiisobutylmethylsilane,-   3-butenyldimethoxyethylsilane,-   3-butenyldimethoxy-n-propylsilane,-   3-butenyldimethoxyisopropylsilane,-   3-butenyldimethoxyn-butylsilane,-   3-butenyldimethoxyisobutylsilane,-   3-butenyldimethoxytert-butylsilane,-   3-butenyldiethoxyethylsilane,-   3-butenyldiethoxyn-propylsilane,-   3-butenyldiethoxyisopropylsilane,-   3-butenyldimethoxyhydrosilane,-   3-butenyldiethoxyhydrosilane,-   3-butenylmethoxydimethylsilane,-   3-butenylethoxydimethylsilane,-   3-butenyl-n-propyldimethylsilane,-   3-butenylisopropyldimethylsilane,-   3-butenyl-n-butyldimethylsilane,-   3-butenylisobutyldimethylsilane,-   3-butenylmethoxydiethylsilane,-   3-butenylmethoxydi-n-propylsilane,-   3-butenylmethoxydiisopropylsilane,-   3-butenylmethoxydi-n-butylsilane,-   3-butenylmethoxyisodibutylsilane,-   3-butenylmethoxytert-butylsilane,-   3-butenylethoxydiethylsilane,-   3-butenylethoxydi-n-propylsilane,-   3-butenylethoxydiisopropylsilane,-   3-butenylmethoxydihydrosilane,-   3-butenylethoxydihydrosilane,-   3-butenyldichloromethylsilane,-   3-butenyldichloroethylsilane,-   3-butenyldichloro-n-propylsilane,-   3-butenyldichloroisopropylsilane,-   3-butenyldichloro-n-butylsilane,-   3-butenyldichloroisobutylsilane,-   3-butenyldichlorotert-butylsilane,-   3-butenyldichlorohydrosilane,-   3-butenylchlorodimethylsilane,-   3-butenylchlorodiethylsilane,-   3-butenylchlorodi-n-propylsilane,-   3-butenylchlorodiisopropylsilane,-   3-butenylchlorodi-n-butylsilane,-   3-butenylchloroisodibutylsilane,-   3-butenylchlorodi-tert-butylsilane,-   3-butenylchlorodihydrosilane,-   4-pentenyldimethoxymethylsilane,-   4-pentenylmethoxydimethylsilane,-   4-pentenyldichloromethylsilane,-   4-pentenylchlorodimethylsilane,-   5-hexenyldimethoxymethylsilane,-   5-hexenylmethoxydimethylsilane,-   5-hexenyldichloromethylsilane,-   5-hexenylchlorodimethylsilane,-   7-octenyldimethoxymethylsilane,-   7-octenylmethoxydimethylsilane,-   7-octenyldichloromethylsilane,-   7-octenylchlorodimethylsilane,-   9-decenyldimethoxymethylsilane,-   9-decenylmethoxydimethylsilane,-   9-decenyldichloromethylsilane,-   9-decenylchlorodimethylsilane,-   11-dodecenyldimethoxymethylsilane,-   11-dodecenylmethoxydimethylsilane,-   11-dodecenyldichloromethylsilane, and-   11-dodeceylchlorodimethylsilane.

Further, examples of the silicon-containing olefin compound of theformula (VII) may include silyl norbornene compounds (silicon-containingolefin compounds) such as:

-   bicyclo[2.2.1]hept-5-ene-2-yldimethoxymethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldiethoxymethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldi-n-propylmethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldiisopropylmethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldi-n-butylmethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldiisobutylmethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldimethoxyethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldimethoxy-n-propylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldimethoxyisopropylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldimethoxy-n-butylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldimethoxyisobutylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldimethoxytert-butylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldiethoxyethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldiethoxy-n-propylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldimethoxyisopropylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldimethoxyhydrosilane,-   bicyclo[2.2.1]hept-5-ene-2-yldiethoxyhydrosilane,-   bicyclo[2.2.1]hept-5-ene-2-ylmethoxydimethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylethoxydimethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yl-n-propyldimethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylisopropyldimethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yl-n-butyldimethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylisobutyldimethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylmethoxydiethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylmethoxydi-n-propylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylmethoxydiisopropylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylmethoxydi-n-butylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylmethoxyisodibuthylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylmethoxydi-tert-buthylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylethoxydiethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylethoxydi-n-propylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylethoxydiisopropylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylmethoxydihydrosilane,-   bicyclo[2.2.1]hept-5-ene-2-ylethoxydihydrosilane,-   bicyclo[2.2.1]hept-5-ene-2-yldichloromethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldichloroethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldichloro-n-propylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldichloroisopropylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldichloro-n-butylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldichloroisobu.tylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldichlorotert-butylsilane,-   bicyclo[2.2.1]hept-5-ene-2-yldichlorohydrosilane,-   bicyclo[2.2.1]hept-5-ene-2-ylchlorodimethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylchlorodiethylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylchlorodi-n-propylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylchlorodiisopropylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylchlorodi-n-butylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylchloroisodibutylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylchlorodi-tert-butylsilane,-   bicyclo[2.2.1]hept-5-ene-2-ylchlorodihydrosilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dimethoxymethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)diethoxymethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)di-n-propylmethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)diisopropylmethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)di-n-butylmethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)diisobutylmethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)di-methoxyethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dimethoxy-n-propylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dimethoxyisopropylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dimethoxy-n-butylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dimethoxyisobutylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dimethoxytert-butylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)diethoxyethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)diethoxy-n-propylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)diethoxyisopropylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dimethoxyhydrosilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)diethoxyhydrosilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)methoxydimethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)ethoxydimethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)n-propyldimethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)isopropyldimethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)n-butyldimethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)isobutyldimethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)methoxydiethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)methoxydi-n-propylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)methoxydi-iso-propylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)methoxydi-n-butylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)methoxyisodibutylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)methoxydi-tert-butylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)ethoxydiethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)ethoxydi-n-propylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)ethoxydiisopropylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)methoxydihydrosilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)ethoxydihydrosilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dichloromethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dichloroethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dichloro-n-propylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dichloroisopropylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dichloro-n-butylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dichloroisobutylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dichlorotert-butylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)dichlorohydrosilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)chlorodimethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)chlorodiethylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)chlorodi-n-propylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)chlorodiisopropylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)chlorodi-n-butylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)chloroisodibutylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)chlorodi-tert-butylsilane,-   (bicyclo[2.2.1]hept-5-ene-2-ylmethyl)chlorodihydrosilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dimethoxymethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)diethoxymethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)di-n-propylmethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)diisopropylmethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)di-n-butylmethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)diisobutylmethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dimethoxyethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dimethoxy-n-propylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dimethoxyisopropylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dimethoxy-n-butylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dimethoxyisobutylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dimethoxytert-butylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)diethoxyethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)di-ethoxy-n-propylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)diethoxyisopropylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dimethoxyhydrosilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)diethoxyhydrosilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)methoxydimethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)ethoxydimethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)n-propyldimethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)isopropyldimethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)n-butyldimethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)isobutyldimethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)methoxydiethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)methoxydi-n-propylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)methoxydiisopropylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)methoxydi-n-butylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)methoxyisodibutylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)methoxydi-tert-butylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)ethoxydiethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)ethoxydi-n-propylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)ethoxydiisopropylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)methoxydihydrosilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)ethoxydihydrosilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dichloromethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dichloroethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dichloro-n-propylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dichloroisopropylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dichloro-n-butylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dichloroisobutylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dichlorotert-butylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)dichlorohydrosilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)chlorodimethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)chlorodiethylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)chlorodi-n-propylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)chlorodiisopropylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)chlorodi-n-butylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)chloroisodibutylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)chlorodi-tert-butylsilane,-   (2-bicyclo[2.2.1]hept-5-ene-2-ylethyl)chlorodihydrosilane,-   (3-bicyclo[2.2.1]hept-5-ene-2-ylpropyl)dimethoxymethylsilane,-   (3-bicyclo[2.2.1]hept-5-ene-2-ylpropyl)methoxydimethylsilane,-   (3-bicyclo[2.2.1]hept-5-ene-2-ylpropyl)dichloromethylsilane,-   (3-bicyclo[2.2.1]hept-5-ene-2-ylpropyl)chlorodimethylsilane,-   (4-bicyclo[2.2.1]hept-5-ene-2-ylbutyl)dimethoxymethylsilane,-   (4-bicyclo[2.2.1]hept-5-ene-2-ylbutyl)methoxydimethylsilane,-   (4-bicyclo[2.2.1]hept-5-ene-2-ylbutyl)dichloromethylsilane,-   (4-bicyclo[2.2.1]hept-5-ene-2-ylbutyl)chlorodimethylsilane,-   (6-bicyclo[2.2.1]hept-5-ene-2-ylhexyl)dimethoxymethylsilane,-   (6-bicyclo[2.2.1]hept-5-ene-2-ylhexyl)methoxydimethylsilane,-   (6-bicyclo[2.2.1]hept-5-ene-2-ylhexyl)dichloromethylsilane,-   (6-bicyclo[2.2.1]hept-5-ene-2-ylhexyl)chlorodimethylsilane,-   (8-bicyclo[2.2.1]hept-5-ene-2-yloctyl)dimethoxymethylsilane,-   (8-bicyclo[2.2.1]hept-5-ene-2-yloctyl)methoxydimethylsilane,-   (8-bicyclo[2.2.1]hept-5-ene-2-yloctyl)dichloromethylsilane,-   (8-bicyclo[2.2.1]hept-5-ene-2-yloctyl)chlorodimethylsilane,-   (10-bicyclo[2.2.1]hept-5-ene-2-yldecyl)dimethoxymethylsilane,-   (10-bicyclo[2.2.1]hept-5-ene-2-yldecyl)methoxydimethylsilane,-   (10-bicyclo[2.2.1]hept-5-ene-2-yldecyl)dichloromethylsilane and-   (10-bicyclo[2.2.1]hept-5-ene-2-yldecyl)chlorodimethylsilane.

In the preparation of the ethylene monomer, dicyclopentadiene having apurity of about 95%, which is produced industrially and commerciallyavailable, can be used. For example, it is industrially produced by amethod such that cyclopentadiene present in a C5 fraction from a naphthacracker, etc is dimerized with heating to convert into dicyclopentadieneand recovered by fractional distillation, and then can be submitted foruse. Furthermore, the dicyclopentadiene industrially produced may bepurified with distillation or the like and then highly purified one maybe used.

The cyclopentadiene used in the preparation of the ethylene monomer canbe easily obtained by thermal decomposing the above dicyclopentadiene.

The reaction of the silicon-containing olefin compound of the formula(VII) with dicyclopentadiene or cyclopentadiene, which are staringmaterials for the second silicon-containing olefin copolymer of thepresent invention, is theoretically a reaction of 1 mol of thesilicon-containing olefin compound of the formula (VII) with 1 mol interms of cyclopentadiene. Furthermore, the reaction can be carried outin an arbitrary molar ratio. It is used in terms of cyclopentadiene inan amount of preferably from 0.01 to 100 mol, more preferably from 0.05to 20 mol and further preferably 0.1 to 10 mol based on 1 mol of thesilicon-containing olefin compound of the formula (VII). Thecyclopentadiene is preferably used in the above amount of from 0.01 to100 mol because the sufficient reaction rate can be secured.

In the present invention, although the reaction proceeds particularlywithout use of a solvent, the solvent may be used in accordance with thenecessity. The kind of the solvent used herein is not particularlylimited as long as the reaction is not inhibited. Examples of thesolvent may include aliphatic hydrocarbons such as pentane, hexane,heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene,xylene, ethylbenzene and cumene; halides such as dichloromethane,chloroform, carbon tetrachloride, tetrachloroethane, chlorobenzene,dichlorobenzene and bromobenzene; ethers such as diethylether,tetrahydrofurane, 1,4-dioxane, ethylene glycol dimethyl ether andethylene glycol diethylether; nitrites such as acetonitrile,propionitrile and benzonitrile; and esters such-as ethyl acetate and thelike. These may be used singly or in a mixture of two or more, and theamount thereof is appropriately selected.

In the present invention, though the temperature in carrying out thereaction depends on whether dicyclopentadiene or cyclopentadiene isreacted with the silicon-containing olefin compound of the formula(VII), the temperature is preferably from 0 to 250° C., more preferably10 to 230° C., further more preferably 20 to 200° C. The temperature ispreferably not lower than 0° C. from the viewpoint of the reaction rate,and it is preferably not higher than 250° C., from the viewpoint of thestability of the starting materials and a resulting product, though theabove reaction can be carried out in the range outside of the above.

In carrying out the reaction of the present invention, the pressure isnot particularly limited and varies in accordance with the kind of thestarting materials. The reaction is usually carried out at a pressure offrom atmospheric pressure to 10 MPa.

The reaction time is preferably from 0.05 to 300 hr, more preferably 0.1to 200 hr, further more preferably 0.2 to 150 hr though the reactiontime varies according to the reaction temperature. The reaction can becarried out in the time range outside of the above. From the viewpointof the yield, the reaction time is preferably not less than 0.05 hr andfrom the viewpoint of attaining the sufficient productivity, it ispreferably not more than 300 hr.

In the reaction of the silicon-containing olefin compound of the formula(VII) with dicyclopentadiene or cyclopentadiene according to the presentinvention, the reaction type is not particularly limited, and thereaction can be carried out by any one of batch-wise, semi-batch-wiseand continuous methods.

For example, there are a reaction method of feeding cyclopentadieneprepared by thermal decomposing dicyclopentadiene into a reactor inwhich the olefin compound of the formula (VII) has been introducedbeforehand, a reaction method of feeding the olefin compound of theformula (VII) and dicyclopnetadiene simultaneously into a reactor, and areaction method of continuously feeding the olefin compound of theformula (VII) and dicyclopnetadiene simultaneously into a reactor whilecontinuously drawing off a reaction liquid mixture.

In the first silicon-containing olefin copolymer of the presentinvention, the molar ratio (ethylene/α-olefin) of ethylene to anα-olefin of 3 to 20 carbon atoms, or the molar ratio (a)/(b) ofconstituent unit derived from (a) —CH₂—CH₂— to constituent unit derivedfrom (b) —CH₂—CHR— has an upper limit of 99/1, preferably 97/3, morepreferably 95/5, further more preferably 92/8. According to decreasingthe ethylene proportion such that the molar ratio varies to 85/15,80/20, 75/25, 70/30, 68/32, the desirable result can be obtained. Themolar ratio (ethylene/α-olefin) has a lower limit of 30/70, preferably40/60, more preferably 50/50, further more preferably 55/45, especially60/40. Specifically, the molar ratio (ethylene/α-olefin) is, forexample, from 99/1 to 30/70, preferably 97/3 to 40/60, more preferably95/5 to 50/50, further more preferably 92/8 to 55/45.

When the ethylene proportion is larger than the above range, a resultingmolded article loses flexibility, on the other hand, when it is smallerthan the above range, a resulting molded article deteriorates in heataging characteristics.

The first and second silicon-containing olefin copolymers according tothe present invention have an intrinsic viscosity [η] as measured indecalin at 135° C., which is not particularly limited, of usually from0.1 to 10 dl/g. In general, the intrinsic viscosity [η] has an upperlimit of preferably 6 dl/g, more preferably 4 dl/g, further morepreferably 3.5 dl/g, still more preferably 2 dl/g. It is preferred thatthe upper limit of the intrinsic viscosity [η] lowes so as to be 1 dl/g,0.7 dl/g and 0.6 dl/g. The intrinsic viscosity [η] has a lower limit ofpreferably 0.2 dl/g, more preferably 0.3 dl/g. When the intrinsicviscosity [η] is in the above range, it is possible to prepare moldedarticles having excellent strength properties and resistance tocompression set and also to prepare a cross-linkable rubber compositionhaving excellent processability. Specifically, the intrinsic viscosity[η] is in the range of from preferably 0.2 to 6 dl/g, more preferably0.3 to 4 dl/g, most preferably 0.3 to 3.5 dl/g. In other preferredembodiment, the intrinsic viscosity [η] is in the range of from 0.1 to 2dl/g, preferably 0.1 to 1 dl/g, more preferably 0.1 to 0.7 dl/g, mostpreferably 0.2 to 0.6 dl/g. The silicon-containing olefin copolymerhaving an intrinsic viscosity [η] in the above range is particularlypreferable as sealing materials, potting materials, coating materialsand adhesives.

The second silicon-containing olefin copolymer of the present inventioncontains the ethylene monomer having the silicon-containing group of theformula (IV) in an amount of from 0.1 to 10 mol %, preferably 0.1 to 5mol %, more preferably 0.1 to 3 mol % based on 100 mol % of the totalamount of ethylene, α-olefin and the ethylene monomer. The firstsilicon-containing olefin copolymer of the present invention containsthe silicon-containing constituent unit having the silicon-containinggroup of the formula (I) in an amount of from 0.1 to 10 mol %,preferably 0.1 to 5 mol %, more preferably 0.1 to 3 mol % based on 100mol % of the total amount of (a) the constituent unit derived from—CH₂—CH₂—, (b) the constituent unit derived from —CH₂—CHR— and thesilicon-containing constituent unit. When the silicon-containingconstituent unit having the silicon-containing group of the formula (I)is in the above range, it is possible to prepare a molded article havingexcellent strength properties and resistance to compression set and alsoto prepare a cross-linkable rubber composition having excellent storagestability.

The first and second silicon-containing olefin copolymers according tothe present invention have a number average molecular weight (Mn) and aniodine value (IV), which satisfy the following formula,

generally IV < 33800/Mn, preferably IV < 25400/Mn, more preferably IV <20000/Mn, further more preferably IV < 17800/Mn, and still morepreferably IV < 15000/Mn

The first and second silicon-containing olefin copolymers have an iodinevalue in the above range can prepare a molded article having excellentheat aging characteristics and also a cross-linkable rubber composition.In particular, in this case, the copolymers are suitable for use ofsealing materials in need of weathering resistance and heat agingcharacteristics.

The first and second silicon-containing olefin copolymers according tothe present invention have a branching index, which is not particularlylimited. The branching index has a lower limit of usually not less than0.70, preferably not less than 0.75, more preferably not less than 0.80,further more preferably not less than 0.85, still more preferably notless than 0.90. In the above range, the branching index is preferablynot less than 0.93, more preferably not less than 0.95, further morepreferably not less than 0.97, especially not less than 0.99.

The branching index has an upper limit, which is not particularlylimited and is generally not more than 1.0, preferably not more than1.00. The first and second silicon-containing olefin copolymers having abranching index in the above range can prepare a silicon-containingolefin copolymer rubber having excellent dynamic fatigue characteristicsand particularly excellent properties as sealing materials. In oneembodiment of the present invention, the first and secondsilicon-containing olefin copolymers have a branching index of from 0.70to 1.0, preferably 0.75 to 1.0, more preferably 0.8 to 1.0.Additionally, the branching index is preferably from 0.85 to 1.0, morepreferably 0.90 to 1.0, further more preferably 0.93 to 1.0, moreoverpreferably 0.95 to 1.0, still more preferably 0.97 to 1.0, mostpreferably 0.99 to 1.0. The first and second silicon-containing olefincopolymers having a branching index in the above range have particularlyexcellent dynamic fatigue characteristics, processability, strength andelongation so that they exhibit excellent properties as sealingmaterials. The branching index can be controlled by selecting thecatalyst as described later.

The first and second silicon-containing olefin copolymers according tothe present invention satisfy the above properties and also have amolecular weight distribution (Mw/Mn), as measured in GPC, of from 1.0to 10, preferably 1.5 to 10, more preferably 1.7 to 5, further morepreferably 1.8 to 4, moreover preferably 1.8 to 3.5. Thesilicon-containing olefin copolymers having a molecular weightdistribution (Mw/Mn) in the above range can prepare a cross-linkablerubber composition having excellent processability and strengthproperties. The first and second silicon-containing olefin copolymersaccording to the present invention are preferably random copolymers.

[Process for Producing the Silicon-containing Olefin Copolymer]

The first and second silicon-containing olefin copolymers (hereinaftersimply referred to as silicon-containing olefin copolymer according tothe present invention) can be synthesized by a metallocene catalyst, ora Ziegler catalyst containing a vanadium compound and an organoaluminumcompound as main components.

Particularly, a metallocene catalyst, which comprises a metallocenecompound of a Group IVB transition metal of the Periodic Table, anorganoaluminum oxy compound and/or an ionized ionic compound ispreferably used as the metallocene compound.

Firstly, the metallocene catalyst is described.

The metallocene compound of a Group 4 transition metal of the PeriodicTable is represented by the following formula (i).MLx  (i)

In the formula (i), M is aGroup 4 transition metal of the PeriodicTable, specifically, zirconium, titanium or hafnium and x is a valenceof a transition metal.

L is a ligand coordinating to a transition metal, and at least one ofthe ligands L is a ligand having a cyclopentadienyl skeleton and theligand having a cyclopentadienyl skeleton may have a substituent.

Examples of the ligand having a cyclopentadienyl skeleton may includealkyl or cycloalkyl-substituted cyclopentadienyl groups such ascyclopentadienyl group, methylcyclopentadienyl group,ethylcyclopentadienyl group, n- or i-propylcyclopentadienyl group, n-,i-, sec- or t-butylcyclopentadienyl group, dimethylcyclopentadienylgroup, trimethylcyclopentadienyl group, tetramethylcyclopentadienylgroup, pentamethylcyclopentadienyl group, methylethylcyclopentadienylgroup, methylpropylcyclopentadienyl group andmethylbutylcyclopentadienyl group, and further may include indenylgroup, 4,5,6,7-tetrahydroindenyl group and fluorenyl group.

These groups may be substituted with a halogen atom or a trialkyl sillylgroup.

Of these, an alkyl-substituted cyclopentadienyl group is particularlypreferred.

When the compound of the formula (i) has two or more groups having acyclopentadienyl skeleton as a ligand L, two of the groups having acyclopentadienyl skeleton may be bonded through an alkylene group suchas ethylene and propylene, a substituted alkylene group such asisopropylidene and diphenyl methylene, a silylene group and asubstituted silylene group such as dimethyl silylene, diphenyl silyleneand methylphenyl silylene.

Examples of L other than the ligands L having a cyclopentadienylskeleton may include a hydrocarbon groups of 1 to 12 carbon atoms,alkoxy groups, aryloxy groups, sulfonic acid containing groups (—SO₃Ra)(wherein Ra is an alkyl group, an alkyl group substituted with a halogenatom, an aryl group or an aryl group substituted with a halogen atom oralkyl group), a halogen atom and a hydrogen atom.

Examples of the halogen atom may include fluorine, chlorine, bromine andiodine.

Examples of the metallocene compounds wherein M is zirconium and atleast two ligands having a cyclopentadienyl skeleton are contained aredescribed below;

-   bis(methylcyclopentadienyl)zirconium dichloride,-   bis(ethylcyclopentadienyl)zirconium dichloride,-   bis(n-propylcyclopentadienyl)zirconium dichloride,-   bis(indenyl)zirconium dichloride and-   bis(4,5,6-tetrahydroindenyl)zirconium dichloride.

Further examples of the metallocene compounds may include compoundsobtainable by replacing a zirconium metal with a titanium metal orhafnium metal in the above compounds.

In the present invention, compounds represented by the following formula(ii) can be also used as the metallocene compound.L¹M¹X₂  (ii)

In the formula, M is a Group 4 metal or lanthanoide metal in thePeriodic Table, L¹ is a derivative of a delocalized π-bonding group andendows a constrained geometrical configuration to the active site of themetal M¹, and X is independently a hydrogen atom, a halogen atom, ahydrocarbon group, silyl group or gelmyl group having 20 or less carbon,silicon or germanium atoms.

Of the compounds of the formula (ii), compounds represented by thefollowing formula (iii) are preferred.

In the formula, M¹ is titanium, zirconium, or hafnium, and X is the sameas in the above.

Cp is π-bonded to M¹, and a substituted cyclopentadienyl group having asubstituent Z.

Z is oxygen, sulfur, boron or a Group 14 element in the Periodic Tablesuch as silicon, germanium or tin, Y is a ligand containing nitrogen,phosphorous, oxygen or sulfur, and Z and Y may form a condensed ringtogether.

Examples of the compound of the formula (iii) may include:

-   [dimethyl(t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)silane]titanium    dichloride,-   [(t-butylamide)(tetramethyl-η⁵-cyclopenta-dienyl)-1,2-ethanediyl]titanium    dichloride,-   [dibenzyl(t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)silane]titanium    dichloride,-   [dimethyl(t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)silane]dibenzyl    titanium,-   [dimethyl(t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)silane]dimethyl    titanium,-   [(t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl]dibenzyl    titanium,-   [(methylamide)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl]dineopentyl    titanium,-   [(phenylphosphide)(tetramethyl-η⁵-cyclopentadienyl)methylene]diphenyl    titanium,-   [dibenzyl(t-butylamide)(tetramethyl-η⁵-cyclopentadienyl)silane]dibenzyl    titanium,-   [dimethyl(benzylamide)(η⁵-cyclopentadienyl)silane]di(trimethylsilyl)titanium,-   [dimethyl(phenylphosphide)(tetramethyl-η⁵-cyclopentadienyl)silane]dibenzyl    titanium,-   [(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyl]dibenzyl titanium,-   [2-η⁵-(tetramethyl-cyclopentadienyl)-1-methylethanolate(2-)]dibenzyl    titanium,-   [2-η⁵-(tetramethyl-cyclopentadienyl)-1-methylethanolate(2-)]dimethyl    titanium,-   [2-((4a,4b,8a,9,9a-η)-9H-fluorene-9-yl)cyclohexanolate(2-)]dimethyl    titanium, and-   [2-((4a,4b,8a,9,9a-η)-9H-fluorene-9-yl)cyclohexanolate(2-)]dibenzyl    titanium.

Further, compounds obtainable by replacing titanium metal with zirconiummetal or hafnium metal in the above compounds may be exemplified.

These metallocene compounds may be used singly or in combination withtwo or more.

In the present invention, as the metallocene compound of the formula(i), it is preferred to use zirconocene compounds where the center metalatom is zirconium and at least two ligands having a cyclopentadienylskeleton are contained.

As the metallocene compounds of the formula (ii) or (iii), the centermetal atom is preferably titanium. Among the above metallocenecompounds, the compounds of the formula (iii) where the center metalatom is titanium are particularly preferred.

The organoaluminum oxy compounds forming the metallocene catalyst may beconventionally known aluminoxane or organoaluminum oxy compoundsinsoluble in benzene.

The ionized ionic compounds forming the metallocene catalyst may includeLewis acid, ionic compounds, etc.

Examples of Lewis acid are compounds represented by BR₃ where R isfluorine or a phenyl group optionally having a substituent such asfluorine, a methyl group or trifluoromethyl group, and may includetrifluoroboron, triphenyl boron, tris(4-fluorophenyl)boron,tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron andtris(3,5-dimethylphenyl)boron.

Examples of the ionic compounds may include trialkyl substitutedammonium salt, N,N-dialkyl anilinium salt, dialkyl ammonium salt,triaryl phosphonium salt, etc.

Specific examples of trialkyl substituted ammonium salt may include:

-   triethyl ammonium tetra(phenyl)boron,-   tripropyl ammonium tetra(phenyl)boron,-   tri(n-butyl)ammonium tetra(phenyl)boron,-   trimethyl ammonium tetra(p-tolyl)boron,-   trimethyl ammonium tetra(o-tolyl)boron,-   tributyl ammonium tetra(pentafluorophenyl)boron,-   tripropyl ammonium tetra(o,p-dimethylphenyl)boron,-   tributyl ammonium tetra(m,m-dimethylphenyl)boron,-   tributyl ammonium tetra(p-trifluoromethylphenyl)boron and-   tri(n-butyl) ammonium tetra(o-tolyl)boron.

Examples of N,N-dialkyl anilinium salt may include:

-   N,N-dimethyl anilinium tetra(phenyl)boron,-   N,N-diethyl anilinium tetra(phenyl)boron and-   N,N-2,4,6-pentamethyl anilinium tetra(phenyl)boron.

Examples of the dialkyl ammonium salt may include: di(1-propyl)ammoniumtetra(pentafluorophenyl)boron and dicyclohexyl ammoniumtetra(phenyl)boron.

Further examples of the ionic compounds may include: triphenyl carbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl aniliniumtetrakis(pentafluorophenyl)borate and ferroceniumtetra(pentafluorophenyl)borate,

In forming the metallocene catalyst, an organoaluminum compound may beused together with the organoaluminum oxy compound and/or the ionizedionic compound.

Examples of the organoaluminum compound may include:

trialkyl aluminums such as trimethyl aluminum, triethyl aluminum andtriisobutyl aluminum;

dialkyl aluminum halides such as dimethyl aluminum chloride, diethylaluminum chloride and diisobutyl aluminum chloride;

alkylaluminum sesquihalides such as methylaluminum sesquichloride,ethylaluminum sesquichloride and butylaluminum sesquichloride;

alkylaluminum dihalides such as methylaluminum dichloride andethylaluminum dichloride;

dialkyl aluminum hydrides such as diethylaluminum hydride anddibutylaluminum hydride; and

alkylaluminum dihydrides such as ethylaluminum dihydride andpropylaluminum dihydride.

In the present invention, ethylene, an α-olefin of 3 to 20 carbon atomsand the above silicon-containing ethylene monomer are generallycopolymerized in the presence of the above metallocene catalyst in aliquid phase. In this copolymerization, a hydrocarbon solvent isgenerally used as a polymerization solvent, and further anα-olefin suchas propylene may be used.

Examples of the hydrocarbon solvent used in the polymerization are:

aliphatic hydrocarbons and halogen derivatives thereof such as pentane,hexane, heptane, octane, decane, dodecane and kerosene;

alicyclic hydrocarbons and halogen derivatives thereof such ascyclohexane, methylcyclopentane and methylcyclohexane;

aromatic hydrocarbons such as benzene, toluene and xylene; and

halogen derivatives thereof such as chlorobenzene and the like.

These solvents may be used singly or in combination with two or more.

Ethylene, an α-olefin of 3 to 20 carbon atoms and the abovesilicon-containing ethylene monomer can be copolymerized by any ofbatch-wise, continuous methods. The copolymerization is preferablycarried out by the continuous method, particularly preferably by thecontinuous method using a mixing vessel type reactor. In carrying outthe copolymerization with the continuous method, the catalyst is used ina concentration as follows.

In the case of using the metallocene catalyst as a catalyst, theconcentration of the metallocene catalyst in the polymerization systemis generally from 0.00005 to 0.1 mmol/L (polymerization volume),preferably 0.0001 to 0.05 mmol/L. The organoaluminum oxy compound is fedin an amount such that the molar ratio of aluminum atom to transitionmetal contained in the metallocene compound in the polymerization system(Al/transition metal) is from 1 to 10000, preferably 10 to 5000.

The ionized ionic compound is fed in an amount such that the molar ratioof ionized ionic compound to metallocene compound in the polymerizationsystem (ionized ionic compound/metallocene compound) is from 0.5 to 30,preferably 1 to 25.

In the case of using the organoaluminum compound, it is used in anamount of usually about from 0 to 5 mmol/L (polymerization volume),preferably about 0 to 2 mmol/L.

In the case of copolymerizing ethylene, an α-olefin of 3 to 20 carbonatoms and the above silicon-containing ethylene monomer in the presenceof the metallocene catalyst, the copolymerization reaction is generallycarried out under such conditions that the temperature is from −20° C.to 150° C., preferably 0° C. to 120° C., more preferably 0° C. to 100°C., the pressure is over 0 kg/cm² and not more than 80 kg/cm²,preferably over 0 kg/cm² and not more than 50 kg/cm². The polymerizationconditions are preferably constant in the continuous method.

The reaction time (average residence time when the copolymerization iscarried out by the continuous method) varies in accordance with theconditions such as catalyst concentration, polymerization temperatureand the like. The reaction time is usually from 5 min to 5 hr,preferably 10 min to 3 hr.

Ethylene, an α-olefin of 3 to 20 carbon atoms and the abovesilicon-containing ethylene monomer are fed to the polymerization systemin an amount such that the silicon-containing olefin copolymer havingthe specific composition as described above is obtained. Additionally,in the copolymerization, a molecular weight modifier such as hydrogenand the like can be also used.

When ethylene, an α-olefin of 3 to 20 carbon atoms and the abovesilicon-containing ethylene monomer are copolymerized in the abovemanner, the silicon-containing olefin copolymer is usually prepared in apolymerization liquid mixture containing the copolymer. Thepolymerization liquid mixture is treated in the usual way and therebythe cross-linkable silicon-containing olefin copolymer according to thepresent invention can be prepared.

Next, the Ziegler catalyst containing a vanadium compound and anorganoaluminum compound as essential components is described.

The vanadium compound of the Ziegler catalyst containing a vanadiumcompound and an organoaluminum compound as essential components is asoluble vanadium compound represented by VO(OR)_(n)X_(3-n) in which R isa hydrocarbon group, X is a halogen atom and n is an integer of 0 to 3,or a vanadium compound represented by VX₄ in which X is a halogen atom.Examples thereof may include vanadium compounds represented by VO(OR)_(a)X_(b) or V(OR)_(c)X_(d) in which R is a hydrocarbon group,0≦a≦3, 0≦b≦3, 2≦a+b≦3, 0≦c≦4, 0≦d≦4, 3≦c+d≦4, and adducts of electrondonors of these vanadium compounds.

Specific examples thereof may include VOCl₃, VO(OC₂H₅)Cl₂, VO(OC₂H₅)₂Cl,VO(O-iso-C₃H₇)Cl₂, VO(O-n-C₄H₉)Cl₂, VO(OC₂H₅)₃, VOBr₃, VCl₄, VOCl₃,VO(O-n-C₄H₉)₃, VCl₃.2OC₆H₁₂OH, etc.

The organoaluminum compound may include organoaluminum compoundsrepresented by R′_(m)AlX′_(3-m) in which R′ is a hydrocarbon group, X′is a halogen atom and m is an integer of 1 to 3. Examples of theorganoaluminum compound may include:

trialkyl aluminums such as triethyl aluminum and tributyl aluminum andthe like;

dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and thelike;

alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide andthe like;

dialkyl aluminum halides such as diethyl aluminum chloride and the like;and

partially halogenated alkyl aluminums, for example, alkyl aluminumsesquihalides such as ethyl aluminum sesquichloride and the like, andalkyl aluminum dihalides such as ethyl aluminum dichloride and the like.

The silicon-containing olefin copolymer of the present invention isobtainable by randomly copolymerizing ethylene, an α-olefin of 3 to 20carbon atoms and the above silicon-containing ethylene monomer at apolymerization temperature of from 30 to 60° C., especially 30 to 59°C., at a polymerization pressure of from 4 to 12 kgf/cm², especially 5to 8 kgf/cm², in the presence of the Ziegler catalyst containing theabove vanadium compound and the organoaluminum compound as essentialcomponents. The copolymerization is preferably carried out in ahydrocarbon medium (for example, the hydrocarbon solvent same as thoseas described in the metallocene catalyst).

The silicon-containing olefin copolymer of the present invention,further, may be graft-modified with a polar monomer, for example, anunsaturated carboxylic acid or derivative thereof (for example, acidanhydride or ester).

Examples of the unsaturated carboxylic acid may include an acrylic acidand methacrylic acid.

Examples of the acid anhydride of the unsaturated carboxylic acid mayinclude maleic anhydride, etc.

Preferable example of the unsaturated carboxylic acid ester may includemethyl acrylate, ethyl acrylate, etc. The graft modifiers (graftmonomers) of the unsaturated carboxylic acid, etc may be used singly orin combination with two or more. In any cases, the graft amount ispreferably not more than 0.1 mol based on 100 g of thesilicon-containing olefin copolymer before the graft modification.

The use of the silicon-containing olefin copolymer having a graft amountin the above range can prepare a rubber composition having excellentfluidity (molding processability) and capable of preparing across-linked rubber molded article having excellent cold resistance.

The graft modified silicon-containing olefin copolymer can be preparedby allowing the unmodified silicon-containing olefin copolymer asdescribed above to react with an unsaturated carboxylic acid or itsderivative in the presence of a radical initiator.

The graft reaction may be carried out in a solution state or in a moltenstate. In the case of carrying out the graft reaction in a molten state,it is most efficient and preferable to conduct the graft reaction in anextruder continuously.

Additionally the following non-conjugated polyene can be copolymerizedas long as the aimed physical properties of the present invention arenot marred, for example the branching index is not less than 0.70. Forexample, the copolymerization with 5-vinyl-2-norbornene, or a diene suchas norbornadiene, 1,7-octadiene and 1,8-nonadiene can decrease thebranching index.

Examples of the non-conjugated polyene may include:

cyclic dienes such as 5-methylene-2-norbornene, 5-vinyl-2-norbornene,5-(2-propenyl)-2-norbornene and 5-(3-butenyl)-2-norbornene;

chainlike non-conjugated dienes such as 1,4-hexadiene and7-methyl-1,6-octadiene;

cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene,5-methylene-2-norbornene, 5-isopropylidene-2-norbornene,5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene anddicyclopentadiene; and

cyclic trienes such as 2,3-diisopropylidene-5-norbornene and the like.These polyene compounds may be used singly or in combination with two ormore. The copolymerization with, for example, 5-vinyl-2-norbornene ordienes such as norbornadiene, 1,7-octadiene and 1,8-nonadiene candecrease the branching index in the range of not less than 0.70.

Cross-Linkable Rubber Composition

The cross-linkable rubber composition of the present invention is acuring composition and may be blended with a catalyst (B) whichaccelerates the hydrolysis, in addition to the above silicon-containingolefin copolymer (component (A)), and further, may optionally contain astabilizer (C), a reinforcing agent (D) and a plasticizer (E).

Catalyst (B)

The catalyst (B) used in the present invention is not particularlylimited as long as it accelerates the hydrolysis. Examples thereof mayinclude:

titanic acid esters such as tetrabutyl titanate and tetrapropyltitanate;

tin carboxylic acid salts such as dibutyl tin dioctoate, dibutyl tindilaurate, dibutyl tin maleate, dibutyl tin diacetate, tin octylic acidand tin naphthenic acid;

a reaction product of dibutyl tin oxide and phthalic acid ester;

dibutyl tin diacetylacetonate;

organoaluminum compounds such as aluminum trisacetylacetonate, aluminumtrisethylacetoacetate and diisopropoxy aluminum ethylacetoacetate;

xylate compounds such as zirconium tetraacetylacetonate and titaniumtetraacetylacetonate;

lead octylate;

amine compounds such as butyl amine, octyl amine, lauryl amine, dibutylamine, monoethanol amine, diethanol amine, triethanol amine, diethylenetriamine, triethylene tetramine, oleyl amine, cyclohexyl amine, benzylamine, diethyl aminopropyl amine, xylylene diamine, triethylene diamine,guanidine, diphenyl guanidiene, 2,4,6-tris(dimethyl aminomethyl)phenol,morpholine, N-methyl morpholine, 2-ethyl-4-methyl imidazole and1,8-diazabicyclo[5.4.0]undecene-7(DBU); or salts of these aminecompounds with a carboxylic acid;

low molecular weight polyamide resins obtainable by excess polyamine anda poly basic acid;

reaction products of excess polyamine and an epoxy compound;

silanol condensation catalysts, e.g. amino group-containing silanecoupling agents such as γ-aminopropyl trimethoxy silane andN-(β-aminoethyl)aminopropyl methyl dimethoxy silane; and

known silanol condensation catalysts such as other acid catalysts andbasic catalysts.

These catalysts (B) may be used singly or in combination with two ormore.

Of these catalysts (B), the titanium catalysts and the tin catalysts arepreferred from the viewpoint of easiness of availability, cost andproperties. For example, there are #918 manufactured by Sankyo OrganicChemicals Co., Ltd and the like.

These catalysts (B) are used in an amount of preferably about from 0.1to 20 parts by weight, more preferably 1 to 10 parts by weight based on100 parts by weight of the silicon-containing olefin copolymer (A). Whenthe amount of the catalyst (B) is too small based on thesilicon-containing olefin copolymer (A), the curing rate is occasionallyslow and the curing reaction does not proceed sufficiently. On the otherhand, when the amount of the catalyst (B) is too large based on thesilicon-containing olefin copolymer (A), local exothermic reaction orbubble forming are induced in curing and good cured products are hardlyprepared. Therefore, the use of the large amount of the catalyst (B) isunfavorable.

Stabilizer (C)

Examples of the stabilizer(C) optionally used in the present inventionmay include a heat stabilizer, weathering stabilizer and hindered aminestabilizer.

Examples of the heat stabilizer optionally used in the present inventionmay include a phenol stabilizer, phosphorus stabilizer and sulfurstabilizer.

As the phenol stabilizer, phenol stabilizers conventionally used as astabilizer can be used without limitation.

Examples of the phenol stabilizer may include

-   β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester,-   tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,-   tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,-   1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-t-hydroxybenzyl)benzene,-   d1-α-tocopherol,-   tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate,-   tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy    ethyl]isocyanurate, and-   3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methyl    phenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5] undecane.

As the phenol stabilizer, commercially available ones can be used.Examples thereof are:

-   Irganox 1010 (Trade Mark, Ciba-Geigy Co.),-   Irganox 1076 (Trade Mark, Ciba-Geigy Co.),-   Irganox 1330 (Trade Mark, Ciba-Geigy Co.),-   Irganox 3114 (Trade Mark, Ciba-Geigy Co.),-   Irganox 3125 (Trade Mark, Ciba-Geigy Co.),-   BHT (Trade Mark, Takeda Chemical Industries Ltd.),-   Cyanox 1790 (Trade Mark Cyanamide Co., Ltd.),    Sumilizer GA-80 (Trade Mark Sumitomo Chemicals Co., Ltd.), and    Vitamin E (Eisai Co., Ltd). These phenol stabilizers may be used    singly or in combination.

The phenol stabilizer is used from 0.01 to 20 parts by weight,preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3 parts byweight based on 100 parts by weight of the silicon-containing olefincopolymer (A). When the phenol stabilizer is used in the above amountsbased on 100 parts by weight of the copolymer (A), the stabilities suchas heat resistant and aging resistant are highly improved, and furtherthe cost of the stabilizer is reduced and the properties of thecopolymer (A) such as tensile strength and the like after a heat agingtest do not lower.

As the phosphorus stabilizers, posphorus stabilizers conventionally usedas a stabilizer are used without particular limitation. Examples of thephosphorus stabilizers may include conventionally available ones, suchas Irgafos 168 (Trade Mark, Ciba-Geigy Co.), Irgafos 12 (Trade Mark,Ciba-Geigy Co.), Irgafos 38 (Trade Mark, Ciba-Geigy Co.), Mark329K(Trade Mark, Asahi Denka Co., Ltd), Mark PEP 36 (Trade Mark, Asahi DenkaCo., Ltd), Mark PEP 8 (Trade Mark, Asahi Denka Co., Ltd), Sandstab P-EPQ(Trade Mark, Clariant AG), Weston 618 (Trade Mark GE Co.), Weston 619(Trade Mark, GE Co.) and Weston 624 (Trade Mark, GE Co.). Thesephosphorus stabilizers may be used singly or in combination.

The phosphorus stabilizer is used in an amount of from 0.01 to 20 partsby weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to3 parts by weight based on 100 parts by weight of the copolymer (A).When the content of the phosphorus stabilizer is in the above rangebased on 100 parts by weight of the copolymer (A), the effect ofimproving the stabilities such as heat resistance and aging resistanceis high, and further the cost of the stabilizer is reduced and theproperties of the copolymer (A) such as tensile strength and the likeafter a heat aging test do not lower.

As the sulfur stabilizer, sulfur stabilizers conventionally used as astabilizer are used without particular limitation. Specifically, thesulfur stabilizer may include dilauryl-, dimyristyl-, distearyl- andother dialkyl-thiodipropionates, or esters of butyl-, octyl-, lauryl-,stearyl- and other alkyl thiopropionic acid with polyvalent alcohols,for example, glycerin, trimethylolethane, trimethylolpropane,pentaerythritol and trishydroxyethylisocyanurate, such aspentaerythritol tetralauryl thiopropionate.

Examples of the sulfur stabilizers may include conventionally availableones, such as DSPT (Trade Mark Yoshitomi Pharmaceutical IndustriesLtd.), DLTP (Trade Mark Yoshitomi Pharmaceutical Industries Ltd.),DLTOIB (Trade Mark Yoshitomi Pharmaceutical Industries Ltd.), DMTP(Trade Mark Yoshitomi Pharmaceutical Industries Ltd.), Seenox 412S(Cyanamid Co.) and Cyanox 1212 (Cyanamid Co.). These sulfur stabilizersmay be used singly or in combination.

The sulfur stabilizer is used in an amount of from 0.01 to 20 parts byweight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 3parts by weight based on 100 parts by weight of the copolymer (A). Whenthe content of the sulfur stabilizer is in the above range based on 100parts by weight of the copolymer (A), the effect of improving thestabilities such as heat resistance and aging resistance is high, andfurther the cost of the stabilizer is reduced and the properties of thecopolymer (A) such as tensile strength and the like after a heat agingtest do not lower.

The weathering stabilizers optionally used in the present invention areclassified into an ultraviolet absorber and a light stabilizer.

Examples of the ultraviolet stabilizer may include a salicylic acidultraviolet absorber, benzophenone ultraviolet absorber, benzotriazoleultraviolet absorber and cyanoacrylate ultraviolet absorber.

The ultraviolet absorber is used in an amount of from 0.01 to 20 partsby weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to3 parts by weight based on 100 parts by weight of the copolymer (A).

As the light stabilizer, conventionally known light stabilizers can beused, and hindered amine light stabilizers (HALS) are preferably usedamong them.

Examples of the hindered amine light stabilizers are the followingcompounds:

-   (1) bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,-   (2) dimethyl    succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl    pyperidine polycondensate,-   (3)    poly{[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triadine-2-4-diyl][(2,2,6,6-tetramethyl-4-pyperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-pyperidyl)imino]},-   (4) tetrakis(2,2,6,6-tetramethyl-4-pyperidyl)-1,2,3,4-butane    tetracarboxylate,-   (5) 1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethyl pyperadinone,-   (6)    mixed{2,2,6,6-tetramethyl-4-pyperidyl/β,β,β′β′-tetramethyl-3-9-[2,4,8,10-tetraoxaspiro(5.5)undecane]diethyl}-1,2,3,4-butane    tetracarboxylate,-   (7)    poly{[6-N-morpholyl-1,3,5-triadine-2-4-diyl][(2,2,6,6-tetramethyl-4-pyperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-pyperidyl)imidno]}    and-   (8) condensate of    N,N′-bis(2,2,6,6-tetramethyl-4-pyperidyl)hexamethylene diamine and    1,2-dibromoethane.

These hindered amine light stabilizers may be used singly or incombination.

The hindered amine light stabilizer is used in an amount of from 0.01 to20 parts by weight, preferably 0.05 to 10 parts by weight, morepreferably 0.1 to 3 parts by weight based on 100 parts by weight of thecopolymer (A). When the content of the hindered amine light stabilizeris in the above range based on 100 parts by weight of the copolymer (A),the effect of improving the stabilities such as heat resistance andaging resistance is high, and further the cost of the light stabilizeris reduced and the properties of the copolymer (A) such as tensilestrength and the like after a weathering resistant test do not lower.

Reinforcing Agent (D)

The reinforcing agent optionally used in the present invention has aneffect of enhancing the mechanical properties of a cross-linked productsuch as tensile strength, tear strength and abrasion resistance.Examples of the reinforcing agent mayincludecarbonblackssuchas SRF, GPF,FEF, HAF, ISAF, SAF, FT, and MT; surface-treated carbon blacks with asilane coupling agent, etc; fine powdery silicic acid and silica.

Specific examples of silica may include fumed silica, precipitatedsilica, etc. These silicas may be surface-treated with a reactive silanesuch as hexamethyl disilazane, chlorosilane, alkoxy silane, etc. or lowmolecular weight siloxane. These silicas have a specific surface area asmeasured by BED method of preferably not less than 50 m²/g, morepreferably from 100 to 400 m²/g.

The kind and the amount of these reinforcing agents (D) areappropriately selected in accordance with the use. The amount of thereinforcing agent (D) is at most 300 parts by weight, preferably at most200 parts by weight based on 100 parts by weight of the copolymer (A).

Plasticizer (E)

The plasticizer (E) optionally used in the present invention is notparticularly limited. Examples of the plasticizer may include phthalicacid esters such as dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl)phthalate, dioctyl phthalate, butyl benzyl phthalate andbutyl phthalyl butyl glycolate;

non-aromatic dibasic acid esters such as dioctyl adipate and dioctylsebacate;

polyalkylene glycol esters such as diethylene glycol dibenzoate andtriethylene glycol dibenzoate;

phosphoric acid esters such as tricresyl phosphate and tributylphosphate;

chlorinated paraffins; and

hydrocarbon oils such as alkyldiphenyl, polybutene,hydrogenatedpolybutene, ethylene-α-olefinoligomer, α-methyl styreneoilgomer, biphenyl, triphenyl, triaryl dimethane, alkylene triphenyl,liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil,naphthene oil, atactic polypropylene and partially hydrogenatedterphenyl. These plasticizers (E) may be used singly or in combination.These plasticizers (E) may be blended in preparing the copolymer (A).

Of these plasticizers (E), the hydrocarbon plasticizer is preferredbecause it is widely used and has a low cost and excellent weatheringresistance.

Other Components

The cross-linkable rubber composition of the present invention may beoptionally blended with various additives such as inorganic fillers,dehydrating agents, tackifiers, physical property regulators, storagestability improvers, antioxidants, metal inactivators, ozonedeterioration inhibitors, amine radical chain inhibitors, phosphorusperoxide decomposing agents, lubricants, pigments and foaming agents.

Examples of the inorganic fillers may include precipitated calciumcarbonate, heavy calcium carbonate, talc and clay.

The kind and the amount of these inorganic fillers are appropriatelyselected in accordance with the use. The amount of the inorganic filleris at most 300 parts by weight, preferably at most 200 parts by weightbased on 100 parts by weight of the copolymer (A).

As the dehydrating agent, compounds capable of reaction with water aregenerally preferred, and particularly a hydrolyzable silicon compound ispreferred. The hydrolyzable silicon compound is a general name for lowmolecular silicon compounds having a hydrolyzable functional groupcapable of reacting in the presence of moisture and, in general, itpreferably has a molecular weight of not more than 300. Additionally,the hydrolyzable silicon compound may include other functional groupsthan the hydrolyzable functional group.

Examples of the hydrolyzable functional group may include alkoxyl group,acyloxy group, ketoxymate group, amino group, aminoxy group, amide groupand alkenyloxy group. Examples of the other functional groups mayinclude epoxy-containing groups, amino-containing groups,acryl-containing groups and mercapto-containing groups. These compoundsare specifically described below:

Further, it is also possible to use an aminosilane compound serving bothas a tackifier and a dehydrating agent.

As the aminosilane compound, the amino group-substituted alkoxysilane oramino group-substituted alkoxy silane derivative compound is exemplifiedmore specifically.

Examples thereof are amino group substituted alkoxysilanes such asH₂NCH₂CH₂CH₂Si(OCH₃)₃, H₂NCH₂CH₂NHCH₂CH₂Si(OCH₃)₃,

and(C₂H₅O)₃SiCH₂CH₂CH₂NHCH₂CH₂—NHCH₂CH₂CH₂Si(OC₂H₅)₃,

reactants of this amino group-substituted alkoxysilane and an epoxysilane compound such as

reactants of the above amino group-substituted alkoxy silane and anacryloyl silane compound such as

The reactants of the amino group-substituted alkoxysilane and the epoxysilane compound or the reactants of the amino group-substituted alkoxysilane and the acryloyl silane compound can be easily prepared by mixing1 mol of the amino group-substituted alkoxy silane and 0.2 to 5 mol ofthe silane compound and stirring at a temperature of from roomtemperature to 180° C. for 1 to 8 hr.

The amino group-substituted alkoxy silane or the amino group-substitutedalkoxy silane derivative compound is preferably used in an amount offrom 0.01 to 20 parts by weight based on 100 parts by weight of thesilicon-containing olefin copolymer (A).

As the adhesion improver, adhesives generally used, silane couplingagents such as aminosilane compounds and epoxy silane compounds, andother compounds are used. Examples of the adhesion improver may includephenol resin, epoxy resin, γ-aminopropyl trimethoxy silane,N-(β-aminoethyl)aminopropyl methyl dimethoxy silane, coumarone-indeneresin, rosin ester resin, terpene-phenol resin,α-methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene,alkyltitanates and aromatic polyisocyanate.

As the storage stability improver, compounds in which hydrolyzable groupis bonded to a silicon atom, and ortho-organic acid esters aredescribed.

Examples of the storage stability improver may includemethyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane,ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane,trimethyl(n-butoxy)silane, n-butyltrimethoxysilane and methylortho-formate.

Examples of the antioxidant may include known antioxidants generallyused, such as sulfur antioxidant, radical inhibitor and ultravioletabsorber.

Examples of the sulfur antioxidant are mercaptans, salts of mercaptans,sulfides including sulfide carboxylates or hindered phenol sulfides,polysulfides, dithio carboxylic acid salts, thioureas, thiophosphates,sulfonium compounds, thioaldehydes, thioketones, mercaptals,mercaptoles, monothioic acids, polythioic acids, thioamides andsulfoxides. Specific examples of sulfur antioxidant may includemercaptans such as 2-mercaptobenzothiazole, salts of mercaptans such aszinc salt of 2-mercatobenzothiazole sulfides such as4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol), polysulfides such as2-benzothiazole disulfide, dithiocarboxylic acid salts such as zincdibutyl dithiocarbamate, thioureas such as1-butyl-3-oxy-diethylene-2-thiourea, thiophosphates such as trilauryltrithiophosphate.

When the sulfur antioxidants are used for the curing composition of thepresent invention, the decomposition deterioration in a main chain ofthe copolymer (A) caused by heat can be greatly prevented and theoccurrence of surface tack (tackiness) can be prevented as compared withother antioxidants.

Examples of the radical inhibitor are phenol radical inhibitors such as2,2-methylene-bis(4-methyl-6-t-butylphenol) andtetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,and amine radical inhibitors such as phenyl-β-naphthyl amine, α-naphthylamine, N,N′-sec-butyl-p-phenylene diamine, phenothiadine andN,N′-diphenyl-p-phenylene diamine.

The ultraviolet absorbers are the same as those described in thestabilizer (C).

In addition to the above various additives, the cross-linkable rubbercomposition of the present invention may be further blended withadditives such as rubber reinforcing agent, softener, processing aid,vulcanization accelerator, organic peroxide, cross-linking assistant,foaming assistant, colorant, dispersant, flame retardant without missingthe scope of the invention.

The rubber-reinforcing agent has an effect of enhancing mechanicalproperties of a cross-linking (vulcanizing) rubber such as tensilestrength, tear strength and abrasion resistance. Examples of therubber-reinforcing agent may include carbon blacks such as SRF, GPF,FEF, HAF, ISAF, SAF, FT and MT; surface-treated carbon blacks with asilane coupling agent; fine powdery silicic acid; and silica.

Specific examples of silica may include fumed silica, precipitatedsilica, etc. These silicas may be surface-treated with a reactive silanesuch as hexamethyl disilazane, chlorosilane, alkoxysilane, etc. or lowmolecular weight siloxane. The silica has a specific surface area asmeasured by BED method of preferably not less than 50 m²/g, morepreferably from 100 to 400 m²/g.

The kind and the amount of these rubber-reinforcing agents areappropriately selected in accordance with the use. The amount of therubber-reinforcing agent is at most 300 parts by weight, preferably atmost 200 parts by weight based on 100 parts by weight of the copolymer(A).

As the softener, softeners generally used for rubbers can be used.Examples thereof are petroleum type softeners such as process oil andfluid paraffin; coal tar type softeners such as coal tar and the like;fatty oil type softeners such as castor oil and the like; tall oil;factice; waxes such as bee wax and the like; aliphatic acids andaliphatic acid salts such as ricinoleic acid, palmitic acid, bariumstearate, calcium stearate and zinc laurate; and synthetic polymers suchas petroleum resin, atactic polypropylene and cumarone-indene resin. Ofthese, the petroleum type softeners are preferably used and process oilis preferably used in particular.

The amount of these softeners is appropriately selected in accordancewith the use of a cross-linked product.

The composition of the present invention contains the silicon-containingolefin copolymer as described above.

To the composition of the present invention, the catalyst (B) may beadded. That is, the composition is a cross-linkable compositioncomprising the silicon-containing olefin copolymer and the catalyst (B).

The composition of the present invention may be optionally blended withat least one of the stabilizer (C), the reinforcing agent (D) and theplasticizer (E).

[Process for Preparing Cross-Linkable Rubber Composition]

The process for preparing the cross-linkable rubber compositionaccording to the present invention is not particularly limited, and mayinclude, for example, a conventional process of blending the abovecomponents, kneading them at room temperature or under heating with akneader or a process of dissolving the components by using a smallamount of a suitable solvent and mixing.

That is to say, the cross-linkable rubber composition according to thepresent invention can be prepared by mixing the silicon-containingolefin copolymer (A) and the catalyst (B), and optionally in accordancewith the use of the aimed cross-linked product, the stabilizer (C), thereinforcing agent (D), the plasticizer (E) and the above additives bymeans of mixers such as planetary mixer, etc. or kneading machines suchas roll and kneader.

In the case of using as sealing materials, potting materials, coatingmaterials or adhesives, the compounded rubber thus prepared has aviscosity, as measured at room temperature at 1 rpm by a B typeviscometer, of not more than 10000 Pa·s, preferably not more than 5000Pa·s, more preferably not more than 3000 Pa·s, further prepferably notmore than 2000 Pa·s, still preferably not more than 1000 Pa·s.Additionally, one liquid type or two liquid type compounds prepared bycombining the above components appropriately can be used as thecompounded rubber.

In measuring the compounded rubber, for the one liquid type compound,the viscosity thereof is measured. In the case of the two liquid typecompound, the two liquids are mixed and thereafter the viscosity can bemeasured. The measurement of the viscosity is preferably carried outwithin 10 min after introducing the catalyst.

The cross-linkable rubber composition thus prepared according to thepresent invention is filled in a gap, kneaded and pasted -betweensubstances, applied on a substance for coating, potted into a substanceor molded into a desired shape by an extrusion molding machine, calendarroll, press, injection molding machine or transfer molding machine withRIM (reaction injection) molding, LIM (liquid injection) molding, etc,and thereafter, allowed to stand at room temperature for proceeding thecross-linking reaction and thereby the aimed cross-linked product can beprepared. Further, heating may be applied to advance the cross-linkingreaction.

When the cross-linkable rubber composition of the present invention isexposed to air, it forms a three-dimensional net structure by a functionof moisture and cured into a solid having rubbery elasticity.

[Use of Cross-Linkable Rubber Composition]

The cross-linkable rubber composition of the present invention, asdescribed above, is suitably used in various ways such as electric andelectronic parts, transporting machines, civil engineering andconstructions, medical treatment or leisure activities.

Examples of the use for the electric and electronic parts may includesealing materials, potting materials, coating materials or adhesives forcircuits or substrates of heavy electrical apparatuses, light electricalappliances or electric and electronic appliances; repairing materialsfor covering electric wire; insulating sealing materials for electricwire joint parts; rolls for OA appliances; oscillation absorbers; andgels or sealing materials for condensers.

The above sealing materials are suitably used as sealing materials forrefrigerators, freezers, washing machines, gas meters, microwave ovens,stream irons or circuit-breakers.

The potting materials are suitably used for potting trans high-voltagecircuits, printed boards, high-voltage transformers with variableresistor, electric insulating parts, semi-conductor parts, conductiveparts, solar cells or fly back transformers for TV.

The coating materials are suitably used for coating circuit elements,such as a hybrid IC; HIC; electrical insulating parts; semi-conductiveparts; conductive parts; modules; printed circuits; ceramic boards;buffer materials for diodes, transistors and bonding wires;semi-conductive elements; and optical fibers for optical communication.

The adhesives are suitably used for bonding cathode-ray tube wedges,electric insulating parts, semi-conductor parts or conductive parts.

The use of the transporting machines may include uses for automobiles,ships, airplanes or railway vehicles.

The use in the automobiles may include sealing materials for gaskets ofautomobile-engine, electric installation parts or oil filters; pottingmaterials for igniter HIC or automobile hybrid IC; coating materials forautomobile body, automobile window glass or engine control substrates;and adhesives for gaskets in oil pans or timing belt covers, moles, headlamp lens, sunroof seals or mirrors.

The use in the ships may include sealing materials for wiring andconnection switching boxes, electric parts or electric wires; andadhesives for electric wires or glasses.

The use in the civil engineering and constructions may include sealantsfor building materials, for example, butt joints in the glass screenmethod of business building construction, joints of glass borders withsash, joints for interior decorations in toilet, lavatory, or showcases,joint for bathtub borders, stretching joints for outside wall ofprefabricated houses and joints for sizing boards; sealing materials forplural layered glass; civil engineering sealants used for repairingroads; paints and adhesives for metals, glasses, stone materials,slates, concrete or tiles; and adhesive sheets, waterproof sheets orvibration proof sheets.

The use in the medical treatment may include rubber stopper formedicine, syringe gaskets or rubber corks for pressure reducing bloodvessel.

The use in the leisure activities may include swimming good materialssuch as swimming caps, diving masks and stopples; and gel buffering partmaterials used for sports shoes, baseball gloves and the like.

Of these uses, the rubber composition is preferably used for sealingmaterials or civil engineering and constructions, particularly sealantsfor civil engineering and constructions. In the uses, partial breakagecaused by the vibration of drive way or wind is occurred with lessfrequency.

Further, for the uses of electric and electronic parts, transportingmachines, civil engineering and constructions, medical treatment orleisure activities, for example, sealing materials, potting materials,coating materials, adhesive, etc, the silicon-containing olefincopolymer (A) preferably has a branching index of not less than 0.70,more preferably in the above-described range from the viewpoint ofdynamic fatigue resistance.

Particularly, in the uses of sealing or civil engineering andconstructions, it is one preferred embodiment that thesilicon-containing olefin copolymer (A) has a branching index of notless than 0.70, for example, from 0.8 to 1. The preferable range of thebranching index is the same as described above.

The silicon-containing olefin copolymer of the present invention can beapplied to not only a two component type room temperature cross-linkablerubber but also a one component type room temperature cross-linkablerubber, and is used for uses such as elastic sealing agents andadhesives and further can be applied to a cross-linking type resinmodifier by mixing with other polyolefins. Particularly, it is preferredto use as a toner modifier, especially a color toner modifier.

To produce a cross-linked article from the cross-linkable rubbercomposition according to the present invention, in similar to generalroom temperature cross-linkable rubbers (RTV rubber), thesilicon-containing olefin copolymer (A), the catalyst (B), andoptionally in accordance with an aimed cross-linked product, thestabilizer (C), the reinforcing agent (D), the plasticizer (E), theinorganic filler and other additives are mixed and then the compoundedrubber is molded into an aimed shape (for example, it is filled betweengaps, pasted into the gap between substrates, applied on a substrate forcoating or potted on a substrate). Thereafter, the molded article isallowed to stand at room temperature to perform cross-linking(vulcanization). Further, heating may be applied in order to acceleratethe cross-linking reaction. Further, molding may be conducted by RIM(reaction injection method) or LIM (liquid injection method). The RIM orLIM molding exhibits the effect in particular.

EXAMPLES

Hereinafter, the present invention will be described with reference tothe following non-limiting examples.

With regard to the copolymers used in the examples and comparativeexamples, the composition, iodine value, intrinsic viscosity [η],branching index and molecular weight distribution (Mw/Mn) are measuredor determined by the following methods.

(1) Composition of Copolymer Rubber

The composition of a copolymer rubber was measured by the ¹³C-NMRmethod.

(2) Iodine Value of Copolymer Rubber

The iodine value of a copolymer rubber was determined by the titrationmethod.

(3) Intrinsic Viscosity [η]

The intrinsic viscosity [η] of a copolymer rubber was measured indecalin at 135° C.

(4) Branching Index

The branching index is an average branching index (BI) and wasdetermined from several values obtained from the following threeexperiments.

(i) Weight average molecular weight (Mw_(LALLS)) measured using the lowangle light scattering method (LALLS) after gel permeationchromatography (GPC).

The weight average molecular weight was measured using a LALLS detectorconnected to a GPC apparatus.

[Measuring Conditions]

-   Appratus: Waters 150 C-   Detector: Chromatix KMX-6-   Column: Shodex UT-806M (30 cm×2 columns), UT-807 (30 cm×1 column)-   Solvent: 1,2,4-trichlorobenzene-   Temperature: 135° C.-   Flow rate: 0.764 ml/min-   Concentration: 0.03 to 0.07% (w/v)-   Injected amount: 300 μl    (ii) Weight average molecular weight (Mw_(DRI)) and viscosity    average molecular weight (Mv_(DRI)) measured using a differential    refractive index detector connected to a GPC apparatus.    [Measuring Conditions]-   Appratus: Waters 150 C-   Detector: DRI (150 C buit-in)-   Column: Shodex UT-806MLT (50 cm×1 column)-   Solvent: 1,2,4-trichlorobenzene-   Temperature: 135° C.-   Flow rate: 1 ml/min-   Concentration: 0.2% (w/v)-   Injected amount: 160 μl

Each of the average molecular weights was determined in terms of thevalue of EPDM. The viscosity formula used for the conversion is asfollows.Intrinsic viscosity [η]=2.92×10⁻⁴ Mw ^(0.726)(iii) Intrinsic viscosity (IV) (=[η]) as measured in decalin at 135° C.

The viscosity at each of four concentration adjustment points wasmeasured with the multipoint method using an Ubbellohde viscometer andthe relation of each of the measuring points was extrapolated to zeroconcentration.

The above measuring values (i) and (ii) were determined with GPC using adiluted 1,2,4-trichlorobenzene solution from which a polymer wasfiltered off.

The average branching index (BI) is defined by the following formula.BI=(Mv _(br) ×Mw _(DRI))/(Mw _(LALLS) ×Mv _(DRI))In the formula, Mv_(br)=k(IV)^(1/a), Mv_(br) is a viscosity averagemolecular weight of a branched polymer, a is a Mark-Houwink constant(ethylene/α-olefin/non-conjugated polyene copolymer has a value, asmeasured at 135° C. in decalin, of 0.759).(5) Molecular Weight Distribution (Mw/Mn)

The molecular weight distribution of a copolymer rubber was representedby a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a numberaverage molecular weight (Mn), as determined with GPC. In the GPC,GMH-HT and GMH-HTL manufactured by Tosoh Coporation were used as acolumn and ortho-dichlorobenzene was used as a solvent.

Production Example 1

[Synthesis of Silicon-Containing Ethylene/Propylene Random CopolymerRubber (A-1)]

A 2 L internal volume separable glass flask equipped with a stirrer wasthoroughly purged with nitrogen, and to the flask, 1450 ml ofimpurity-removed hexane and 0.375 ml of 1-methyldimethoxysilyl-ethylnorbornene(=(bicyclo[2.2.1]-5-ene-2-yl)dimethoxyethylsilane) were fed at 23° C.Successively, 6 ml of a diluted hexane solution of 12 mmol of ethylaluminum sesquichloride was fed. Thereafter, this glass separable flaskwas heated in a stream of nitrogen. When the temperature reached to 40°C., the stream of nitrogen was stopped, and then hydrogen, ethylene andpropylene were passed through, in an amount of 10 NL/hr, 85 NL/hr and 65NL/hr respectively.

Subsequently, 24 ml of a hexane solution of 1.2 mmol of VO(OC₂H₅)Cl₂ wasintroduced into the flask over 2 sec from a dropping funnel andpolymerization was carried out at 40° C. for 10 min. Thereafter, 5 g ofmethanol was introduced into the separable glass flask to stop thepolymerization.

The resulting polymerization solution was introduced into 200 ml ofmethanol and was stirred for 5 min, and then was allowed to stand for 60min. Subsequently, the solid component present in the bottom of theflask and the green solution were separated. Thereafter, thepolymerization solution was introduced into 2000 ml of acetone toprepare a polymer containing the solvent.

Subsequently, the solvent containing polymer was dried under reducedpressure at 130° C. for 8 hr at a 600 mmHg and thereby 4.5 g of asilicon-containing ethylene/propylene random copolymer rubber (A-1) wasobtained.

The copolymer rubber (A-1) had an intrinsic viscosity [η] of 0.5 dl/g, amolar ratio of ethylene to propylene of 68/32, a branching index of0.98, a Mw/Mn of 3 and a content of an ethylene monomer having asilicon-containing group of 0.3 mol % (silicon content 0.3 mol %).

Subsequently, to 100 g of the copolymer rubber (A-1), 100 g of aplasticizer [Trade Mark PW-32 manufactured by Idemitsu Kosan Co., Ltd]was added and completely dissolved with mixing at 80° C. for 3 hr toprepare a copolymer (B-1). The silicon content of the silicon-containingcopolymer (B-1) was measured and found to be 0.3 mol %.

Preparation Example 2

[Synthesis of Silyl Group-ContainingEthylene/Propylene/5-vinyl-2-norbornene Random Copolymer Rubber (A-2)]

Continuous terpolymerization of ethylene, propylene and5-vinyl-2-norbornene was carried out using a 100 L internal volumestainless steel polymerization reactor equipped with a stirrer blade(rotation speed=250 rpm). From the side inlet of the polymerizationreactor into a liquid phase, 60 L/hr of hexane, 3.0 Kg/hr of ethylene,9.0 Kg/hr of propylene, 550g/hr of 5-vinyl-2-norbornene, and further 60L/hr of hydrogen, and as a catalyst, 95 mmol/hr of VOCl₃, 443 mmol/hr ofAl(Et)₂Cl and 127 mmol of Al(Et)_(1.5)Cl_(1.5) were fed continuously.

Carrying out the terpolymerization reaction in the conditions asdescribed above, an ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-2) was obtained in a homogeneous solution state.

Thereafter, to the polymerization solution continuously drawn out fromthe lower part of the polymerization reactor, a small amount of methanolwas added to stop the polymerization reaction. After the polymer wasseparated from a solvent with a steam stripping, the polymer was driedin vacuo at 55° C. for 48 hr.

Consequently, a copolymer rubber (A-2) having a molar ratio of ethyleneto propylene of 68/32, an intrinsic viscosity [η] of 0.5 dl/g, an iodinevalue of 10 g/100 g, a branching index of 0.7, a Mw/Mn of 20 wasobtained in an amount of 4.5 Kg/h.

To 100 g of the copolymer rubber (A-2), 100 g of a plasticizer [TrandeMark PW-32 manufactured by Idemitsu Kosan Co., Ltd] was added andcompletely dissolved with mixing at 80° C. for 3 hr. Thereafter, thetemperature was returned to room temperature, 0.07 g of a catalyst[platinum-divinyltetramethyldisiloxane complex, Trade Mark SIP6832.0manufactured by GELEST. Inc.: vinyl end group containingpolydimethylsiloxane solution having a 3% platinum concentration] and1.5 g of dimethoxymethylsilane [Trade Mark TSL8117 manufactured by GEToshiba silicon Co., Ltd.] were fed and reacted at 120° C. for 2 hr.After the reaction, the silicon content of the silyl group modifiedcopolymer rubber (B-2) was measured and found to be 0.3 mol %. Thismeans the fact that in the silyl group modified copolymer rubber (B-2),0.3 mol % of the structure derived from 5-vinyl-2-norbornene constituentunits modified with silyl group was contained based on 100 mol % of thetotal of the constituent units of the rubber (B-2).

Example 1

Firstly, 200 parts by weight of the silicon-containingethylene/propylene random copolymer rubber (B-1) prepared in PreparationExample 1, 100 parts by weight of calcium carbonate [Trade Mark KALFAIN200 manufactured by Maruo Calcium Co., Ltd.], 60 parts by weight of aplasticizer [Trade mark PW-32 manufacture by Idemitsu Kosan Co., Ltd.],2 parts by weight of a dehydrating agent [Trade Name A-171 manufacturedby Nippon Unicar Co., Ltd.], 2 parts by weight of an adhesive [TradeMark A-1100 manufactured by Nippon Unicar Co., Ltd.], 1 part by weightof an antioxidant [Trade Name Irganox 1010 manufactured by Ciba-GeigyCo., 1 part by weight of an ultraviolet absorber [Trade Mark Tinubin 327manufactured by Ciba-Geigy Co.] and 1 part by weight of a weatheringstabilizer [Trade Mark Sanol LS770 manufactured by Sankyo Lifetech. Co.,Ltd.] were kneaded at 120° C. in vacuo by means of a planetary mixer[manufactured by INOUE MFG. CO.] to prepared a compounded rubber (C-1).

The resulting compounded rubber (C-1) was kneaded with 2 parts by weightof a catalyst [Trade Mark #918 manufactured by Sankyo Chemicals Inc.] bya planetary mixer [manufactured by INOUE MFG. CO.] at room temperaturein vacuo to prepare a compounded rubber (D-1).

Using the resulting compounded rubber, the viscosity of the compoundedrubber was measured in accordance with JIS K7117 (1997). The results areshown in Table 1. The compounded rubber had a viscosity, as measuredwith a B type viscometer at 0.01 rpm, of 8,000,000 cPs, and a viscosityas measured at 1 rpm of 265 Pa·s.

Using the compounded rubber, a tensile test piece was prepared andsubjected to a tensile test in accordance with JIS A1439(1997). Further,it was subjected to de Mattia flexing fatigue test in accordance withJIS K-6260(1999). The de Mattia flexing fatigue test is an index of lifeof products toward external vibration, for example, sealing materials.These results are shown in Table 1.

(1) Tensile Test

The tensile test was carried out at a measuring temperature of 23° C. ata tensile rate of 500 mm/min in accordance with JIS K6251, and the breakstrength TB and the elongation at break EB of cross-linked sheet weremeasured.

(2) de Mattia Flexing Fatigue Test

The de Mattia flexing fatigue test was carried out in accordance withJIS-K-6260 (1999) and the number of flexings until a crack was grown to15 mm was measured.

Comparative Example 1

The procedure of Example 1 was repeated except that in place of thecopolymer rubber (B-1), the silyl group contaningethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (B-2)prepared in Preparation Example 2 was used. The results are shown inTable 1. In this case, the copolymer rubber (B-2) had a branching indexof 0.65.

Using a resulting compounded rubber, the viscosity of the compoundedrubber was measured in accordance with JIS K7117(1997) in the samemanner as in Example 1. The results are shown in Table 1. The compoundedrubber had a viscosity, as measured with a B type viscometer at 0.01rpm, of 13,500,000 cPs, and a viscosity as measured at 1 rpm of 330Pa·s.

TABLE 1 Comparative Example 1 Example 1 Silyl group-containing copolymerrubber (B-1) (B-2) Properties of Silyl group-containing copolymer rubberEthylene/α-olefin (molar ratio) 68/32 68/32 Kind of α-olefin propylenepropylene Silicon content (mol %) 0.3 0.3 Iodine value (g/100 g) 0.7 10[η] (dl/g) 0.5 0.5 Mw/Mn 3 20 Branching Idex 0.98 0.65 Amount of oilextension (phr) 100 100 33800/Mn 1.33 7.98 Composition of Compound (partby weight) Copolymer (each as described above) 200 200 Calcium carbonate100 100 Plasticizer 60 60 Dehydrating agent 2 2 Adhesive 2 2 Antioxidant1 1 Ultraviolet absorber 1 1 Weathering stabilizer 1 1 Catalyst 2 2Viscosity of Compounded rubber (B type viscometer) Viscosity (cPs) at0.01 rpm 8,000,000 13,500,000 Properties of Cross-linked rubber TB (MPa)0.55 0.45 EB (%) 550 190 Dymanic fatigue resistance Not less 10² deMattia flexing fatigue test then 10³ Number of flexing until a crack wasgrown to 15 mm

INDUSTRIAL APPLICABILITY

The silicon-containing olefin copolymer of the present invention can beused in a cross-linked state and has a high cross-linking rate, andexcellent productivity, heat aging resistance, weathering resistance,and also can prepare molded articles having excellent properties such asscratch resistance, resistance to compressive set, electric propertiesand strength.

The cross-linkable rubber composition of the present invention comprisesthe above copolymer so that it can be cross-linked and submitted to use.Further it has a high cross-linking rate, and excellent productivity,heat aging resistance, weathering resistance, and also can preparemolded articles (cross-linked products) having excellent properties suchas scratch resistance, resistance to compressive set, electricproperties and strength.

Therefore, the cross-linkable rubber composition of the presentinvention can be suitably applied for uses such as electric andelectronic parts, transporting machines, civil engineering andconstructions, medical treatment or leisure activities. Further, therubber composition of the present invention can be cured at roomtemperature or at a low temperature so that it is useful to uses, forexample, sealing materials, potting materials, coating materials, andadhesives, and further is useful to covering compositions used forairplanes, constructions, automobiles and glass, sealing compositions,and surface-treating agents for various inorganic materials.

The cross-linked article of the present invention is obtainable bycross-linking the above rubber composition so that it has excellent heatageing properties and weathering properties, and also excellent scratchresistance, resistance to compression set, electric properties, strengthand other properties.

1. A silicon-containing olefin copolymer comprising: (a) a constituentunit derived from —CH₂—CH₂—, (b) a constituent unit derived from—CH₂—CHR— where R is a hydrocarbon group of 1 to 18 carbon atoms, and(c) a constituent unit represented by the following formula (I)

 wherein k is 0, 1 or 2, A is a hydrogen atom or a hydrocarbon group of1 to 6 carbon atoms, B is a single bond or a hydrocarbon group of 1 to20 carbon atoms, X, Y and Z are each independently selected from thegroup consisting of a hydrocarbon group of 1 to 6 carbon atoms, alkoxygroup of 1 to 6 carbon atoms, acyloxy group, ketoximate group, amidegroup, acid amide group, aminoxy group, thioalkoxy group and aminogroup, at least one of X, Y and Z is selected from the group consistingof an alkoxy group of 1 to 6 carbon atoms, acyloxy group, ketoximategroup, amide group, acid amide group, and aminoxy group; and having: (i)a molar ratio (a)/(b) of the constituent unit (a) to the constituentunit (b) of from 99/1 to 30/70, (ii) a content of the constituent unit(c) of from 0.1 to 10 mol % based on 100 mol % of the total amounts ofthe constituent units (a), (b) and (c), and (iii) a branching index ofnot less than 0.70.
 2. The silicon-containing olefin copolymer accordingto claim 1 wherein the constituent unit (c) is represented by theformula (I) in which k is 0, A is a hydrogen atom and B is representedby —(CR¹R²)_(n)—, wherein the constituent unit (c) is represented by thefollowing formula (II):

wherein n is an integer of 0 to 10, R¹ and R² each are independently ahydrogen atom or an alkyl group of 1 to 3 carbon atoms, and when n is 2or more, the plural groups R¹ may be identical or different each otherand the plural groups R² may be also identical or different each other.3. The silicon-containing olefin copolymer according to claim 1 whereinthe constituent unit (c) is represented by the formula (I) in which k is1, A is a hydrogen atom and B is represented by —(CR¹R²)_(n)—, whereinthe constituent unit (c) is represented by the following formula (III):

wherein n is an integer of 0 to 10, R¹ and R² each are independently ahydrogen atom or an alkyl group of 1 to 3 carbon atoms, and when n is 2or more, the plural groups R¹ may be identical or different each otherand the plural groups R² may be also identical or different each other.4. A silicon-containing olefin copolymer which is cross-linkable andobtainable by copolymerizing ethylene, an α-olefin of 3 to 20 carbonatoms and an ethylene monomer having a silicon-containing grouprepresented by the following formula (IV):—Si(X)(Y)(Z)  (IV) wherein X, Y, and Z are each independently selectedfrom the group consisting of a hydrocarbon group of 1 to 6 carbon atoms,alkoxy group of 1 to 6 carbon atoms, acyloxy group, ketoximate group,amide group, acid amide group, aminoxy group, thioalkoxy group and aminogroup, at least one of X, Y and Z is selected from the group consistingof an alkoxy group of 1 to 6 carbon atoms, acyloxy group, ketoximategroup, amide group, acid amide group, and aminoxy group; and whichcopolymer has: (i) a molar ratio of ethylene to α-olefin of 3 to 20carbon atoms of from 99/1 to 30/70, (ii) a content of the ethylenemonomer having a silicon-containing group of from 0.1 to 10 mol % basedon 100 mol % of the total amounts of ethylene, α-olefin and the ethylenemonomer having a silicon-containing group of the formula (IV), and (iii)a branching index of not less than 0.70.
 5. The silicon-containingolefin copolymers according to claim 1 which has an intrinsic viscosityη, as measured in decalin at 135° C., of from 0.1 to 10 dl/g.
 6. Thesilicon-containing olefin copolymers according to claim 1 whichsatisfies the following formula:IV<33800/Mn wherein Mn is a number average molecular weight and IV is aniodine value.
 7. A cross-linkable rubber composition comprising asilicon-containing olefin copolymer according to claim
 1. 8. The rubbercomposition according to claim 7 used in electric and electronic parts,transporting machines, civil engineering and constructions, medicaltreatment or leisure activities.
 9. The rubber composition according toclaim 7 used for sealing materials, potting materials, coating materialsand adhesives.
 10. A sealing material, potting material, coatingmaterial or adhesive comprising a rubber composition according to claim7.
 11. A cross-linked product obtainable by cross-linking a rubbercomposition according to claim 7.